CN103097433B - The method preparing polyether carbonate polyol - Google Patents
The method preparing polyether carbonate polyol Download PDFInfo
- Publication number
- CN103097433B CN103097433B CN201180035162.3A CN201180035162A CN103097433B CN 103097433 B CN103097433 B CN 103097433B CN 201180035162 A CN201180035162 A CN 201180035162A CN 103097433 B CN103097433 B CN 103097433B
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- China
- Prior art keywords
- metal
- mol
- oxide
- carbonate
- cyanide
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- -1 carbonate polyol Chemical class 0.000 title claims abstract description 122
- 229920000570 polyether Polymers 0.000 title claims abstract description 68
- 239000004721 Polyphenylene oxide Substances 0.000 title claims abstract description 65
- 229920005862 polyol Polymers 0.000 title claims abstract description 64
- 238000000034 method Methods 0.000 title claims abstract description 37
- 239000003054 catalyst Substances 0.000 claims abstract description 90
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 claims abstract description 88
- 229910052751 metal Inorganic materials 0.000 claims abstract description 69
- 239000002184 metal Substances 0.000 claims abstract description 69
- 229910002092 carbon dioxide Inorganic materials 0.000 claims abstract description 64
- 239000000126 substance Substances 0.000 claims abstract description 56
- 239000007858 starting material Substances 0.000 claims abstract description 54
- 239000001569 carbon dioxide Substances 0.000 claims abstract description 44
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 claims abstract description 41
- 125000002947 alkylene group Chemical group 0.000 claims abstract description 40
- 239000003513 alkali Substances 0.000 claims abstract description 32
- 150000002825 nitriles Chemical class 0.000 claims abstract description 32
- 150000004706 metal oxides Chemical group 0.000 claims abstract description 22
- 229910000000 metal hydroxide Inorganic materials 0.000 claims abstract description 18
- 150000004692 metal hydroxides Chemical class 0.000 claims abstract description 18
- 150000003839 salts Chemical class 0.000 claims abstract description 12
- 230000002194 synthesizing effect Effects 0.000 claims abstract description 11
- 239000000203 mixture Substances 0.000 claims description 52
- 239000002253 acid Substances 0.000 claims description 35
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 35
- 239000007864 aqueous solution Substances 0.000 claims description 34
- 150000001875 compounds Chemical class 0.000 claims description 32
- 230000004913 activation Effects 0.000 claims description 30
- 238000006243 chemical reaction Methods 0.000 claims description 29
- 239000000243 solution Substances 0.000 claims description 28
- JMANVNJQNLATNU-UHFFFAOYSA-N oxalonitrile Chemical compound N#CC#N JMANVNJQNLATNU-UHFFFAOYSA-N 0.000 claims description 24
- 238000005406 washing Methods 0.000 claims description 20
- 238000007334 copolymerization reaction Methods 0.000 claims description 19
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 18
- 229910044991 metal oxide Inorganic materials 0.000 claims description 17
- 239000000376 reactant Substances 0.000 claims description 17
- 239000007787 solid Substances 0.000 claims description 14
- JIAARYAFYJHUJI-UHFFFAOYSA-L zinc dichloride Chemical compound [Cl-].[Cl-].[Zn+2] JIAARYAFYJHUJI-UHFFFAOYSA-L 0.000 claims description 14
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 claims description 13
- 229910052700 potassium Inorganic materials 0.000 claims description 13
- 239000011591 potassium Substances 0.000 claims description 13
- 239000000725 suspension Substances 0.000 claims description 13
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims description 10
- 239000003999 initiator Substances 0.000 claims description 10
- 239000011701 zinc Substances 0.000 claims description 10
- 229910052725 zinc Inorganic materials 0.000 claims description 10
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 9
- WXBFPUDKHADDKC-UHFFFAOYSA-N [Co+3].N#CC#N Chemical compound [Co+3].N#CC#N WXBFPUDKHADDKC-UHFFFAOYSA-N 0.000 claims description 9
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 8
- VNDYJBBGRKZCSX-UHFFFAOYSA-L zinc bromide Chemical compound Br[Zn]Br VNDYJBBGRKZCSX-UHFFFAOYSA-L 0.000 claims description 8
- 235000013495 cobalt Nutrition 0.000 claims description 7
- 239000011592 zinc chloride Substances 0.000 claims description 7
- 235000005074 zinc chloride Nutrition 0.000 claims description 7
- 229910052799 carbon Inorganic materials 0.000 claims description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 claims description 5
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 4
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims description 4
- 238000001035 drying Methods 0.000 claims description 4
- 229910052739 hydrogen Inorganic materials 0.000 claims description 4
- 239000001257 hydrogen Substances 0.000 claims description 4
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 claims description 4
- 229940102001 zinc bromide Drugs 0.000 claims description 4
- UAYWVJHJZHQCIE-UHFFFAOYSA-L zinc iodide Chemical compound I[Zn]I UAYWVJHJZHQCIE-UHFFFAOYSA-L 0.000 claims description 4
- ONDPHDOFVYQSGI-UHFFFAOYSA-N zinc nitrate Chemical compound [Zn+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O ONDPHDOFVYQSGI-UHFFFAOYSA-N 0.000 claims description 4
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 3
- 238000005660 chlorination reaction Methods 0.000 claims description 3
- 230000006837 decompression Effects 0.000 claims description 3
- XFXPMWWXUTWYJX-UHFFFAOYSA-N Cyanide Chemical compound N#[C-] XFXPMWWXUTWYJX-UHFFFAOYSA-N 0.000 claims description 2
- ZOIORXHNWRGPMV-UHFFFAOYSA-N acetic acid;zinc Chemical compound [Zn].CC(O)=O.CC(O)=O ZOIORXHNWRGPMV-UHFFFAOYSA-N 0.000 claims description 2
- UNRQTHVKJQUDDF-UHFFFAOYSA-N acetylpyruvic acid Chemical compound CC(=O)CC(=O)C(O)=O UNRQTHVKJQUDDF-UHFFFAOYSA-N 0.000 claims description 2
- RQPZNWPYLFFXCP-UHFFFAOYSA-L barium dihydroxide Chemical compound [OH-].[OH-].[Ba+2] RQPZNWPYLFFXCP-UHFFFAOYSA-L 0.000 claims description 2
- 229910001863 barium hydroxide Inorganic materials 0.000 claims description 2
- QVQLCTNNEUAWMS-UHFFFAOYSA-N barium oxide Inorganic materials [Ba]=O QVQLCTNNEUAWMS-UHFFFAOYSA-N 0.000 claims description 2
- CSSYLTMKCUORDA-UHFFFAOYSA-N barium(2+);oxygen(2-) Chemical compound [O-2].[Ba+2] CSSYLTMKCUORDA-UHFFFAOYSA-N 0.000 claims description 2
- AXCZMVOFGPJBDE-UHFFFAOYSA-L calcium dihydroxide Chemical compound [OH-].[OH-].[Ca+2] AXCZMVOFGPJBDE-UHFFFAOYSA-L 0.000 claims description 2
- 239000000920 calcium hydroxide Substances 0.000 claims description 2
- 229910001861 calcium hydroxide Inorganic materials 0.000 claims description 2
- BRPQOXSCLDDYGP-UHFFFAOYSA-N calcium oxide Chemical compound [O-2].[Ca+2] BRPQOXSCLDDYGP-UHFFFAOYSA-N 0.000 claims description 2
- 239000000292 calcium oxide Substances 0.000 claims description 2
- ODINCKMPIJJUCX-UHFFFAOYSA-N calcium oxide Inorganic materials [Ca]=O ODINCKMPIJJUCX-UHFFFAOYSA-N 0.000 claims description 2
- GVPFVAHMJGGAJG-UHFFFAOYSA-L cobalt dichloride Chemical compound [Cl-].[Cl-].[Co+2] GVPFVAHMJGGAJG-UHFFFAOYSA-L 0.000 claims description 2
- INDBQWVYFLTCFF-UHFFFAOYSA-L cobalt(2+);dithiocyanate Chemical compound [Co+2].[S-]C#N.[S-]C#N INDBQWVYFLTCFF-UHFFFAOYSA-L 0.000 claims description 2
- 229940097267 cobaltous chloride Drugs 0.000 claims description 2
- 238000010438 heat treatment Methods 0.000 claims description 2
- 229910000358 iron sulfate Inorganic materials 0.000 claims description 2
- BAUYGSIQEAFULO-UHFFFAOYSA-L iron(2+) sulfate (anhydrous) Chemical compound [Fe+2].[O-]S([O-])(=O)=O BAUYGSIQEAFULO-UHFFFAOYSA-L 0.000 claims description 2
- KBJMLQFLOWQJNF-UHFFFAOYSA-N nickel(ii) nitrate Chemical compound [Ni+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O KBJMLQFLOWQJNF-UHFFFAOYSA-N 0.000 claims description 2
- 230000000737 periodic effect Effects 0.000 claims description 2
- 229910000027 potassium carbonate Inorganic materials 0.000 claims description 2
- 229910000029 sodium carbonate Inorganic materials 0.000 claims description 2
- FEONEKOZSGPOFN-UHFFFAOYSA-K tribromoiron Chemical compound Br[Fe](Br)Br FEONEKOZSGPOFN-UHFFFAOYSA-K 0.000 claims description 2
- 239000004246 zinc acetate Substances 0.000 claims description 2
- JDLYKQWJXAQNNS-UHFFFAOYSA-L zinc;dibenzoate Chemical compound [Zn+2].[O-]C(=O)C1=CC=CC=C1.[O-]C(=O)C1=CC=CC=C1 JDLYKQWJXAQNNS-UHFFFAOYSA-L 0.000 claims description 2
- QMMRZOWCJAIUJA-UHFFFAOYSA-L nickel dichloride Chemical compound Cl[Ni]Cl QMMRZOWCJAIUJA-UHFFFAOYSA-L 0.000 claims 3
- JAWGVVJVYSANRY-UHFFFAOYSA-N cobalt(3+) Chemical compound [Co+3] JAWGVVJVYSANRY-UHFFFAOYSA-N 0.000 claims 1
- 239000002244 precipitate Substances 0.000 claims 1
- DKGAVHZHDRPRBM-UHFFFAOYSA-N Tert-Butanol Chemical compound CC(C)(C)O DKGAVHZHDRPRBM-UHFFFAOYSA-N 0.000 description 73
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 description 66
- ATUOYWHBWRKTHZ-UHFFFAOYSA-N Propane Chemical compound CCC ATUOYWHBWRKTHZ-UHFFFAOYSA-N 0.000 description 56
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 36
- 239000001294 propane Substances 0.000 description 28
- 239000012153 distilled water Substances 0.000 description 26
- 150000003077 polyols Chemical class 0.000 description 26
- 238000002347 injection Methods 0.000 description 24
- 239000007924 injection Substances 0.000 description 24
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 21
- 239000006185 dispersion Substances 0.000 description 19
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 16
- LGRDAQPMSDIUQJ-UHFFFAOYSA-N tripotassium;cobalt(3+);hexacyanide Chemical compound [K+].[K+].[K+].[Co+3].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-] LGRDAQPMSDIUQJ-UHFFFAOYSA-N 0.000 description 16
- 150000002118 epoxides Chemical class 0.000 description 15
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 15
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 14
- 229920001451 polypropylene glycol Polymers 0.000 description 14
- 239000000047 product Substances 0.000 description 13
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 12
- 150000002148 esters Chemical class 0.000 description 11
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 description 10
- 239000000463 material Substances 0.000 description 10
- 229960005082 etohexadiol Drugs 0.000 description 9
- ZMZDMBWJUHKJPS-UHFFFAOYSA-N hydrogen thiocyanate Natural products SC#N ZMZDMBWJUHKJPS-UHFFFAOYSA-N 0.000 description 9
- 125000002462 isocyano group Chemical group *[N+]#[C-] 0.000 description 9
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 description 8
- 150000005676 cyclic carbonates Chemical class 0.000 description 8
- 238000001914 filtration Methods 0.000 description 8
- 229910052736 halogen Inorganic materials 0.000 description 8
- RUOJZAUFBMNUDX-UHFFFAOYSA-N propylene carbonate Chemical compound CC1COC(=O)O1 RUOJZAUFBMNUDX-UHFFFAOYSA-N 0.000 description 8
- 150000005846 sugar alcohols Polymers 0.000 description 8
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 7
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 description 7
- 239000006227 byproduct Substances 0.000 description 7
- 150000001768 cations Chemical class 0.000 description 7
- 239000012065 filter cake Substances 0.000 description 7
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 6
- 239000003795 chemical substances by application Substances 0.000 description 6
- 229910052757 nitrogen Inorganic materials 0.000 description 6
- 229920000642 polymer Polymers 0.000 description 6
- 238000002360 preparation method Methods 0.000 description 6
- 238000000926 separation method Methods 0.000 description 6
- 238000003756 stirring Methods 0.000 description 6
- GTACSIONMHMRPD-UHFFFAOYSA-N 2-[4-[2-(benzenesulfonamido)ethylsulfanyl]-2,6-difluorophenoxy]acetamide Chemical compound C1=C(F)C(OCC(=O)N)=C(F)C=C1SCCNS(=O)(=O)C1=CC=CC=C1 GTACSIONMHMRPD-UHFFFAOYSA-N 0.000 description 5
- 101710130081 Aspergillopepsin-1 Proteins 0.000 description 5
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 5
- 102100031007 Cytosolic non-specific dipeptidase Human genes 0.000 description 5
- 239000004593 Epoxy Substances 0.000 description 5
- ZJCCRDAZUWHFQH-UHFFFAOYSA-N Trimethylolpropane Chemical compound CCC(CO)(CO)CO ZJCCRDAZUWHFQH-UHFFFAOYSA-N 0.000 description 5
- 150000001412 amines Chemical class 0.000 description 5
- BTANRVKWQNVYAZ-UHFFFAOYSA-N butan-2-ol Chemical compound CCC(C)O BTANRVKWQNVYAZ-UHFFFAOYSA-N 0.000 description 5
- 230000000694 effects Effects 0.000 description 5
- 235000019197 fats Nutrition 0.000 description 5
- JBFHTYHTHYHCDJ-UHFFFAOYSA-N gamma-caprolactone Chemical compound CCC1CCC(=O)O1 JBFHTYHTHYHCDJ-UHFFFAOYSA-N 0.000 description 5
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 5
- XMBWDFGMSWQBCA-UHFFFAOYSA-M iodide Chemical compound [I-] XMBWDFGMSWQBCA-UHFFFAOYSA-M 0.000 description 5
- 229940006461 iodide ion Drugs 0.000 description 5
- 239000007788 liquid Substances 0.000 description 5
- 238000002156 mixing Methods 0.000 description 5
- 229910052760 oxygen Inorganic materials 0.000 description 5
- 229920000909 polytetrahydrofuran Polymers 0.000 description 5
- ZEMPKEQAKRGZGQ-AAKVHIHISA-N 2,3-bis[[(z)-12-hydroxyoctadec-9-enoyl]oxy]propyl (z)-12-hydroxyoctadec-9-enoate Chemical compound CCCCCCC(O)C\C=C/CCCCCCCC(=O)OCC(OC(=O)CCCCCCC\C=C/CC(O)CCCCCC)COC(=O)CCCCCCC\C=C/CC(O)CCCCCC ZEMPKEQAKRGZGQ-AAKVHIHISA-N 0.000 description 4
- AIDLAEPHWROGFI-UHFFFAOYSA-N 2-methylbenzene-1,3-dicarboxylic acid Chemical compound CC1=C(C(O)=O)C=CC=C1C(O)=O AIDLAEPHWROGFI-UHFFFAOYSA-N 0.000 description 4
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 4
- VTLYFUHAOXGGBS-UHFFFAOYSA-N Fe3+ Chemical compound [Fe+3] VTLYFUHAOXGGBS-UHFFFAOYSA-N 0.000 description 4
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 4
- WCUXLLCKKVVCTQ-UHFFFAOYSA-M Potassium chloride Chemical compound [Cl-].[K+] WCUXLLCKKVVCTQ-UHFFFAOYSA-M 0.000 description 4
- 150000001450 anions Chemical class 0.000 description 4
- 230000015572 biosynthetic process Effects 0.000 description 4
- WERYXYBDKMZEQL-UHFFFAOYSA-N butane-1,4-diol Chemical compound OCCCCO WERYXYBDKMZEQL-UHFFFAOYSA-N 0.000 description 4
- 230000008859 change Effects 0.000 description 4
- 235000014113 dietary fatty acids Nutrition 0.000 description 4
- IEJIGPNLZYLLBP-UHFFFAOYSA-N dimethyl carbonate Chemical compound COC(=O)OC IEJIGPNLZYLLBP-UHFFFAOYSA-N 0.000 description 4
- SZXQTJUDPRGNJN-UHFFFAOYSA-N dipropylene glycol Chemical compound OCCCOCCCO SZXQTJUDPRGNJN-UHFFFAOYSA-N 0.000 description 4
- GHLKSLMMWAKNBM-UHFFFAOYSA-N dodecane-1,12-diol Chemical compound OCCCCCCCCCCCCO GHLKSLMMWAKNBM-UHFFFAOYSA-N 0.000 description 4
- 239000000194 fatty acid Substances 0.000 description 4
- 229930195729 fatty acid Natural products 0.000 description 4
- 150000004665 fatty acids Chemical class 0.000 description 4
- SLCVBVWXLSEKPL-UHFFFAOYSA-N neopentyl glycol Chemical compound OCC(C)(C)CO SLCVBVWXLSEKPL-UHFFFAOYSA-N 0.000 description 4
- 239000001301 oxygen Substances 0.000 description 4
- 229940059574 pentaerithrityl Drugs 0.000 description 4
- WXZMFSXDPGVJKK-UHFFFAOYSA-N pentaerythritol Chemical compound OCC(CO)(CO)CO WXZMFSXDPGVJKK-UHFFFAOYSA-N 0.000 description 4
- WYURNTSHIVDZCO-UHFFFAOYSA-N tetrahydrofuran Substances C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 4
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 3
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 description 3
- 244000025254 Cannabis sativa Species 0.000 description 3
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 3
- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical group C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 description 3
- LSDPWZHWYPCBBB-UHFFFAOYSA-N Methanethiol Chemical compound SC LSDPWZHWYPCBBB-UHFFFAOYSA-N 0.000 description 3
- VEQPNABPJHWNSG-UHFFFAOYSA-N Nickel(2+) Chemical compound [Ni+2] VEQPNABPJHWNSG-UHFFFAOYSA-N 0.000 description 3
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- PTFCDOFLOPIGGS-UHFFFAOYSA-N Zinc dication Chemical compound [Zn+2] PTFCDOFLOPIGGS-UHFFFAOYSA-N 0.000 description 3
- 150000001335 aliphatic alkanes Chemical class 0.000 description 3
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 description 3
- 229910052794 bromium Inorganic materials 0.000 description 3
- 238000004140 cleaning Methods 0.000 description 3
- XLJKHNWPARRRJB-UHFFFAOYSA-N cobalt(2+) Chemical compound [Co+2] XLJKHNWPARRRJB-UHFFFAOYSA-N 0.000 description 3
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- 239000007789 gas Substances 0.000 description 3
- 238000005227 gel permeation chromatography Methods 0.000 description 3
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 3
- 229910052737 gold Inorganic materials 0.000 description 3
- 239000010931 gold Substances 0.000 description 3
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 3
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- 238000012545 processing Methods 0.000 description 3
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 description 3
- 229910052717 sulfur Inorganic materials 0.000 description 3
- RMVRSNDYEFQCLF-UHFFFAOYSA-N thiophenol Chemical compound SC1=CC=CC=C1 RMVRSNDYEFQCLF-UHFFFAOYSA-N 0.000 description 3
- PUPZLCDOIYMWBV-UHFFFAOYSA-N (+/-)-1,3-Butanediol Chemical compound CC(O)CCO PUPZLCDOIYMWBV-UHFFFAOYSA-N 0.000 description 2
- BBMCTIGTTCKYKF-UHFFFAOYSA-N 1-heptanol Chemical compound CCCCCCCO BBMCTIGTTCKYKF-UHFFFAOYSA-N 0.000 description 2
- 238000005160 1H NMR spectroscopy Methods 0.000 description 2
- BDLXTDLGTWNUFM-UHFFFAOYSA-N 2-[(2-methylpropan-2-yl)oxy]ethanol Chemical compound CC(C)(C)OCCO BDLXTDLGTWNUFM-UHFFFAOYSA-N 0.000 description 2
- PNWSHHILERSSLF-UHFFFAOYSA-N 4-methylbenzene-1,3-dicarboxylic acid Chemical compound CC1=CC=C(C(O)=O)C=C1C(O)=O PNWSHHILERSSLF-UHFFFAOYSA-N 0.000 description 2
- PAYRUJLWNCNPSJ-UHFFFAOYSA-N Aniline Chemical compound NC1=CC=CC=C1 PAYRUJLWNCNPSJ-UHFFFAOYSA-N 0.000 description 2
- CPELXLSAUQHCOX-UHFFFAOYSA-M Bromide Chemical compound [Br-] CPELXLSAUQHCOX-UHFFFAOYSA-M 0.000 description 2
- FERIUCNNQQJTOY-UHFFFAOYSA-N Butyric acid Chemical compound CCCC(O)=O FERIUCNNQQJTOY-UHFFFAOYSA-N 0.000 description 2
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 2
- XTHFKEDIFFGKHM-UHFFFAOYSA-N Dimethoxyethane Chemical compound COCCOC XTHFKEDIFFGKHM-UHFFFAOYSA-N 0.000 description 2
- 239000005977 Ethylene Substances 0.000 description 2
- RRHGJUQNOFWUDK-UHFFFAOYSA-N Isoprene Chemical compound CC(=C)C=C RRHGJUQNOFWUDK-UHFFFAOYSA-N 0.000 description 2
- YNAVUWVOSKDBBP-UHFFFAOYSA-N Morpholine Chemical compound C1COCCN1 YNAVUWVOSKDBBP-UHFFFAOYSA-N 0.000 description 2
- AMQJEAYHLZJPGS-UHFFFAOYSA-N N-Pentanol Chemical compound CCCCCO AMQJEAYHLZJPGS-UHFFFAOYSA-N 0.000 description 2
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- 230000009918 complex formation Effects 0.000 description 1
- 239000000470 constituent Substances 0.000 description 1
- 239000002537 cosmetic Substances 0.000 description 1
- ZXIJMRYMVAMXQP-UHFFFAOYSA-N cycloheptene Chemical compound C1CCC=CCC1 ZXIJMRYMVAMXQP-UHFFFAOYSA-N 0.000 description 1
- IFDVQVHZEKPUSC-UHFFFAOYSA-N cyclohex-3-ene-1,2-dicarboxylic acid Chemical group OC(=O)C1CCC=CC1C(O)=O IFDVQVHZEKPUSC-UHFFFAOYSA-N 0.000 description 1
- ZWAJLVLEBYIOTI-UHFFFAOYSA-N cyclohexene oxide Chemical compound C1CCCC2OC21 ZWAJLVLEBYIOTI-UHFFFAOYSA-N 0.000 description 1
- FWFSEYBSWVRWGL-UHFFFAOYSA-N cyclohexene oxide Natural products O=C1CCCC=C1 FWFSEYBSWVRWGL-UHFFFAOYSA-N 0.000 description 1
- URYYVOIYTNXXBN-UPHRSURJSA-N cyclooctene Chemical compound C1CCC\C=C/CC1 URYYVOIYTNXXBN-UPHRSURJSA-N 0.000 description 1
- 239000004913 cyclooctene Substances 0.000 description 1
- 230000006378 damage Effects 0.000 description 1
- 230000009849 deactivation Effects 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 239000003599 detergent Substances 0.000 description 1
- AQEFLFZSWDEAIP-UHFFFAOYSA-N di-tert-butyl ether Chemical compound CC(C)(C)OC(C)(C)C AQEFLFZSWDEAIP-UHFFFAOYSA-N 0.000 description 1
- 150000005690 diesters Chemical class 0.000 description 1
- ODADONMDNZJQMW-UHFFFAOYSA-N diethoxy-ethyl-[3-(oxiran-2-ylmethoxy)propyl]silane Chemical compound CCO[Si](CC)(OCC)CCCOCC1CO1 ODADONMDNZJQMW-UHFFFAOYSA-N 0.000 description 1
- XBDQKXXYIPTUBI-UHFFFAOYSA-N dimethylselenoniopropionate Natural products CCC(O)=O XBDQKXXYIPTUBI-UHFFFAOYSA-N 0.000 description 1
- 238000005553 drilling Methods 0.000 description 1
- 230000009977 dual effect Effects 0.000 description 1
- XSQNOFMFKVYSNL-UHFFFAOYSA-N ethene;toluene Chemical group C=C.CC1=CC=CC=C1 XSQNOFMFKVYSNL-UHFFFAOYSA-N 0.000 description 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- 239000004744 fabric Substances 0.000 description 1
- 235000019253 formic acid Nutrition 0.000 description 1
- 238000009472 formulation Methods 0.000 description 1
- 239000002816 fuel additive Substances 0.000 description 1
- 229940074391 gallic acid Drugs 0.000 description 1
- 235000004515 gallic acid Nutrition 0.000 description 1
- ZEMPKEQAKRGZGQ-XOQCFJPHSA-N glycerol triricinoleate Natural products CCCCCC[C@@H](O)CC=CCCCCCCCC(=O)OC[C@@H](COC(=O)CCCCCCCC=CC[C@@H](O)CCCCCC)OC(=O)CCCCCCCC=CC[C@H](O)CCCCCC ZEMPKEQAKRGZGQ-XOQCFJPHSA-N 0.000 description 1
- 125000003055 glycidyl group Chemical group C(C1CO1)* 0.000 description 1
- VOZRXNHHFUQHIL-UHFFFAOYSA-N glycidyl methacrylate Chemical compound CC(=C)C(=O)OCC1CO1 VOZRXNHHFUQHIL-UHFFFAOYSA-N 0.000 description 1
- 229930182470 glycoside Natural products 0.000 description 1
- 150000002338 glycosides Chemical class 0.000 description 1
- 239000005431 greenhouse gas Substances 0.000 description 1
- 150000002367 halogens Chemical class 0.000 description 1
- 125000005842 heteroatom Chemical group 0.000 description 1
- IPCSVZSSVZVIGE-UHFFFAOYSA-N hexadecanoic acid Chemical compound CCCCCCCCCCCCCCCC(O)=O IPCSVZSSVZVIGE-UHFFFAOYSA-N 0.000 description 1
- 150000002402 hexoses Chemical class 0.000 description 1
- 235000003642 hunger Nutrition 0.000 description 1
- 150000002431 hydrogen Chemical class 0.000 description 1
- 235000019447 hydroxyethyl cellulose Nutrition 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 239000011261 inert gas Substances 0.000 description 1
- 239000004615 ingredient Substances 0.000 description 1
- 230000002401 inhibitory effect Effects 0.000 description 1
- 208000014674 injury Diseases 0.000 description 1
- 239000002563 ionic surfactant Substances 0.000 description 1
- WLXLKUWDWKQINM-UHFFFAOYSA-N iridium oxalonitrile Chemical compound N#CC#N.[Ir] WLXLKUWDWKQINM-UHFFFAOYSA-N 0.000 description 1
- FBAFATDZDUQKNH-UHFFFAOYSA-M iron chloride Chemical compound [Cl-].[Fe] FBAFATDZDUQKNH-UHFFFAOYSA-M 0.000 description 1
- 239000001282 iso-butane Substances 0.000 description 1
- 235000013847 iso-butane Nutrition 0.000 description 1
- QXJSBBXBKPUZAA-UHFFFAOYSA-N isooleic acid Natural products CCCCCCCC=CCCCCCCCCC(O)=O QXJSBBXBKPUZAA-UHFFFAOYSA-N 0.000 description 1
- QQVIHTHCMHWDBS-UHFFFAOYSA-N isophthalic acid Chemical group OC(=O)C1=CC=CC(C(O)=O)=C1 QQVIHTHCMHWDBS-UHFFFAOYSA-N 0.000 description 1
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 1
- 150000002576 ketones Chemical class 0.000 description 1
- 239000003446 ligand Substances 0.000 description 1
- KQQKGWQCNNTQJW-UHFFFAOYSA-N linolenic acid Natural products CC=CCCC=CCC=CCCCCCCCC(O)=O KQQKGWQCNNTQJW-UHFFFAOYSA-N 0.000 description 1
- 229960004488 linolenic acid Drugs 0.000 description 1
- 229910052744 lithium Inorganic materials 0.000 description 1
- 239000000314 lubricant Substances 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- UCAOGXRUJFKQAP-UHFFFAOYSA-N n,n-dimethyl-5-nitropyridin-2-amine Chemical compound CN(C)C1=CC=C([N+]([O-])=O)C=N1 UCAOGXRUJFKQAP-UHFFFAOYSA-N 0.000 description 1
- DUWWHGPELOTTOE-UHFFFAOYSA-N n-(5-chloro-2,4-dimethoxyphenyl)-3-oxobutanamide Chemical compound COC1=CC(OC)=C(NC(=O)CC(C)=O)C=C1Cl DUWWHGPELOTTOE-UHFFFAOYSA-N 0.000 description 1
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical group CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 1
- QQZOPKMRPOGIEB-UHFFFAOYSA-N n-butyl methyl ketone Natural products CCCCC(C)=O QQZOPKMRPOGIEB-UHFFFAOYSA-N 0.000 description 1
- 239000002736 nonionic surfactant Substances 0.000 description 1
- QIQXTHQIDYTFRH-UHFFFAOYSA-N octadecanoic acid Chemical compound CCCCCCCCCCCCCCCCCC(O)=O QIQXTHQIDYTFRH-UHFFFAOYSA-N 0.000 description 1
- OQCDKBAXFALNLD-UHFFFAOYSA-N octadecanoic acid Natural products CCCCCCCC(C)CCCCCCCCC(O)=O OQCDKBAXFALNLD-UHFFFAOYSA-N 0.000 description 1
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 1
- ZQPPMHVWECSIRJ-KTKRTIGZSA-N oleic acid Chemical compound CCCCCCCC\C=C/CCCCCCCC(O)=O ZQPPMHVWECSIRJ-KTKRTIGZSA-N 0.000 description 1
- 235000021313 oleic acid Nutrition 0.000 description 1
- 150000002894 organic compounds Chemical class 0.000 description 1
- 125000000962 organic group Chemical group 0.000 description 1
- 150000002902 organometallic compounds Chemical class 0.000 description 1
- 235000006408 oxalic acid Nutrition 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 235000021017 pears Nutrition 0.000 description 1
- DPBLXKKOBLCELK-UHFFFAOYSA-N pentan-1-amine Chemical compound CCCCCN DPBLXKKOBLCELK-UHFFFAOYSA-N 0.000 description 1
- 150000003053 piperidines Chemical class 0.000 description 1
- 229920001983 poloxamer Polymers 0.000 description 1
- 229920000191 poly(N-vinyl pyrrolidone) Polymers 0.000 description 1
- 229920001446 poly(acrylic acid-co-maleic acid) Polymers 0.000 description 1
- 229920000233 poly(alkylene oxides) Polymers 0.000 description 1
- 229920002432 poly(vinyl methyl ether) polymer Polymers 0.000 description 1
- 229920002401 polyacrylamide Polymers 0.000 description 1
- 229920000058 polyacrylate Polymers 0.000 description 1
- 239000004584 polyacrylic acid Substances 0.000 description 1
- 229920002239 polyacrylonitrile Polymers 0.000 description 1
- 229920000573 polyethylene Polymers 0.000 description 1
- 229920001228 polyisocyanate Polymers 0.000 description 1
- 239000005056 polyisocyanate Substances 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 229920006324 polyoxymethylene Polymers 0.000 description 1
- 229920002223 polystyrene Polymers 0.000 description 1
- 239000011496 polyurethane foam Substances 0.000 description 1
- 229920002689 polyvinyl acetate Polymers 0.000 description 1
- 239000011118 polyvinyl acetate Substances 0.000 description 1
- YLLIGHVCTUPGEH-UHFFFAOYSA-M potassium;ethanol;hydroxide Chemical compound [OH-].[K+].CCO YLLIGHVCTUPGEH-UHFFFAOYSA-M 0.000 description 1
- 238000004313 potentiometry Methods 0.000 description 1
- 239000002243 precursor Substances 0.000 description 1
- 238000003825 pressing Methods 0.000 description 1
- 150000003141 primary amines Chemical class 0.000 description 1
- TVDSBUOJIPERQY-UHFFFAOYSA-N prop-2-yn-1-ol Chemical compound OCC#C TVDSBUOJIPERQY-UHFFFAOYSA-N 0.000 description 1
- HCOKJWUULRTBRS-UHFFFAOYSA-N propan-2-yloxysilane Chemical compound CC(C)O[SiH3] HCOKJWUULRTBRS-UHFFFAOYSA-N 0.000 description 1
- 235000019260 propionic acid Nutrition 0.000 description 1
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 1
- VTGOHKSTWXHQJK-UHFFFAOYSA-N pyrimidin-2-ol Chemical compound OC1=NC=CC=N1 VTGOHKSTWXHQJK-UHFFFAOYSA-N 0.000 description 1
- 229920005604 random copolymer Polymers 0.000 description 1
- 230000004044 response Effects 0.000 description 1
- HFHDHCJBZVLPGP-UHFFFAOYSA-N schardinger α-dextrin Chemical compound O1C(C(C2O)O)C(CO)OC2OC(C(C2O)O)C(CO)OC2OC(C(C2O)O)C(CO)OC2OC(C(O)C2O)C(CO)OC2OC(C(C2O)O)C(CO)OC2OC2C(O)C(O)C1OC2CO HFHDHCJBZVLPGP-UHFFFAOYSA-N 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 229910000679 solder Inorganic materials 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 239000000600 sorbitol Substances 0.000 description 1
- 239000008117 stearic acid Substances 0.000 description 1
- 239000005720 sucrose Substances 0.000 description 1
- YBRBMKDOPFTVDT-UHFFFAOYSA-N tert-butylamine Chemical compound CC(C)(C)N YBRBMKDOPFTVDT-UHFFFAOYSA-N 0.000 description 1
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 1
- UFDHBDMSHIXOKF-UHFFFAOYSA-N tetrahydrophthalic acid Chemical group OC(=O)C1=C(C(O)=O)CCCC1 UFDHBDMSHIXOKF-UHFFFAOYSA-N 0.000 description 1
- LFQCEHFDDXELDD-UHFFFAOYSA-N tetramethyl orthosilicate Chemical compound CO[Si](OC)(OC)OC LFQCEHFDDXELDD-UHFFFAOYSA-N 0.000 description 1
- 150000003568 thioethers Chemical class 0.000 description 1
- ZIBGPFATKBEMQZ-UHFFFAOYSA-N triethylene glycol Chemical compound OCCOCCOCCO ZIBGPFATKBEMQZ-UHFFFAOYSA-N 0.000 description 1
- BPSIOYPQMFLKFR-UHFFFAOYSA-N trimethoxy-[3-(oxiran-2-ylmethoxy)propyl]silane Chemical compound CO[Si](OC)(OC)CCCOCC1CO1 BPSIOYPQMFLKFR-UHFFFAOYSA-N 0.000 description 1
- 238000010200 validation analysis Methods 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C68/00—Preparation of esters of carbonic or haloformic acids
- C07C68/04—Preparation of esters of carbonic or haloformic acids from carbon dioxide or inorganic carbonates
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G64/00—Macromolecular compounds obtained by reactions forming a carbonic ester link in the main chain of the macromolecule
- C08G64/20—General preparatory processes
- C08G64/32—General preparatory processes using carbon dioxide
- C08G64/34—General preparatory processes using carbon dioxide and cyclic ethers
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G65/00—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule
- C08G65/02—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring
- C08G65/26—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring from cyclic ethers and other compounds
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G65/00—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule
- C08G65/02—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring
- C08G65/26—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring from cyclic ethers and other compounds
- C08G65/2603—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring from cyclic ethers and other compounds the other compounds containing oxygen
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G65/00—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule
- C08G65/02—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring
- C08G65/26—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring from cyclic ethers and other compounds
- C08G65/2642—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring from cyclic ethers and other compounds characterised by the catalyst used
- C08G65/2645—Metals or compounds thereof, e.g. salts
- C08G65/2663—Metal cyanide catalysts, i.e. DMC's
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Health & Medical Sciences (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Inorganic Chemistry (AREA)
- Toxicology (AREA)
- Polyethers (AREA)
- Polyesters Or Polycarbonates (AREA)
Abstract
The present invention relates to a kind of method being prepared polyether carbonate polyol by one or more H functional starter substances, one or more alkylene oxides and carbon dioxide in the presence of at least one DMC catalysts, wherein comprise the alkali equivalent (based on 1 mol based on the metal cyanide salt synthesizing this catalyst) of 0.3 to 1.8 mol of metal hydroxides, metal carbonate and/or the metal oxide form of alkalescence by the cyanide-free slaine preparing DMC catalysts, metal cyanide salt or above-mentioned both salt.
Description
The present invention relates to a kind of in the presence of at least one DMC catalysts, by one or more H-officials can
Beginning material (Startsubstanz), one or more alkylene oxides and carbon dioxide prepare the method for polyether carbonate polyol, its
In for preparing the cyanide-free slaine of DMC catalysts, metal cyanide salt or above-mentioned both salt comprise alkali
The alkali equivalent of 0.3 to 1.8 mol of metal hydroxides, metal carbonate and/or the metal oxide form of property is (based on 1
Mol based on the metal cyanide salt synthesizing this catalyst).
By alkylene oxide (epoxide) and carbon dioxide in the presence of being with or without H-functional starter substance (starting material)
Catalytic reaction prepare polyether carbonate polyol concentrated research more than 40 years (such as Inoue et al.,
Copolymerization of Carbon Dioxide and Epoxide with Organometallic Compounds;
Die Makromolekulare Chemie 130,210-220,1969).Such as use this of H-functional initiator compound
Reaction schematically display in scheme (I), wherein R represents organic group, such as alkyl, alkylaryl or aryl, and it can also
Comprising hetero atom, such as O, S, Si etc., wherein e and f represents integer, for display in the scheme (I) of polyether carbonate polyol
Product be interpreted as that the block with shown structure can be looked in principle in gained polyether carbonate polyol again simply
Arrive, institute during simply the OH degree of functionality of the order of block, quantity and length and starting material can change and be not limited to scheme (I)
The polyether carbonate polyol shown.This reaction (seeing scheme (I)) is ecological highly beneficial because this reaction mean by
Such as CO2Greenhouse gases transform into polymer.Cyclic carbonate shown in formula (I) is (such as R=CH3, isopropyl two
Alcohol carbonic ester) be formed as another kind of product, it is actually by-product.
Within the scope of the present invention, activation represents wherein optionally at CO2In the presence of, the oxirane compounds of partial amount is added
In dmc catalyst, then interrupt adding the step of oxirane compounds, as the result of follow-up heat-producing chemical reaction instead
Answer and device is observed heat release (this can produce temperature peak (" focus ")), and as alkylene oxide and optional CO2The result of reaction,
Observe pressure drop.Activation processing step be from by the oxirane compounds of partial amount optionally at CO2In the presence of join DMC and urge
In agent until heat release occur time period.Generally, dry dmc catalyst under activation step can be placed on intensification and/or decompression
Before the step of optional starting material, within the scope of the present invention, drying steps is not a part for activation step.
Formed copolymer known already by epoxide (such as expoxy propane) and carbon dioxide.Such as, US
4500704 describe carbon dioxide and the copolymerization of expoxy propane using dmc catalyst.Here, such as, from initial substance and 12.3
The expoxy propane (212 mmol) of g and the pressure carbon dioxide of 48 bar start, at 35 DEG C, in the reactor after 48 hours
Convert the expoxy propane of 71%.By the expoxy propane of 150.5 mmol converted, 27 mmol (18%) reaction is formed generally
Undesirable by-product propylene carbonate.
A kind of open method of WO-A 2006/103213, by means of the method, reduces the formation of cyclic carbonate.This point
By adding parent CO in dmc catalyst2Material (such as perfluorochemical) realizes.Even at the high CO of 62 bar2Under pressure
Also low propylene carbonate content is obtained.It is therefoie, for example, the propylene carbonate content in the embodiment 6 of the disclosure thing
It is only 2.7%, but the polydispersity of 7.98 is the highest.
Because propylene carbonate has the highest boiling point (240 DEG C) at ambient pressure, so itself and reactant mixture
Separation be expensive and time-consuming.It is therefore desirable that research and develop a kind of method making epoxide and carbon dioxide copolymerization, its
The amount of the cyclic carbonate (such as propylene carbonate) of middle formation is the least.Therefore, it is an object of the invention to provide
A kind of method, by the method, can (i.e. the ratio of linear polyether carbonic ester to the greatest extent may be used by cyclic carbonate with the selectivity improved
Can low) prepare polyether carbonate polyol, copolymerization wherein occurs the (" time in table 1 waiting time before temperature peak
1 ") it is believed that less than 120 minutes.The shorter waiting time has beneficial effect to the economy of method.
Unexpectedly, it has now been found that above-mentioned purpose by means of one in the presence of at least one dmc catalyst by a kind of or many
Kind H-functional starter substance, one or more alkylene oxides and carbon dioxide are prepared the method for polyether carbonate polyol and are able to reality
Existing, wherein for prepare the cyanide-free slaine of dmc catalyst, metal cyanide salt or above-mentioned both salt comprise 0.3 to
1.8 mol, preferably 0.6 to 1.6 mol, particularly preferred 0.8 to the 1.4 mol (gold for synthesizing this catalyst based on 1 mol
Belong to cyanide salt meter) the alkali equivalent of metal hydroxides, metal carbonate and/or metal oxide form of alkalescence.
Within the scope of the present invention, the alkali equivalent reason of metal hydroxides, metal carbonate and/or the metal-oxide of alkalescence
Solve in the water of metal hydroxides, metal carbonate and/or metal-oxide for the alkalescence used and will be completely dissociated lower gained hydrogen
The equivalent of oxygen radical ion.Such as, the metal carbonate of 0.5 mol produces the alkali equivalent of 1.0 mol.
One preferred embodiment of the present invention be a kind of in the presence of at least one dmc catalyst by one or more H-
The method that functional starter substance, one or more alkylene oxides and carbon dioxide prepare polyether carbonate polyol, it is characterised in that
By in the presence of one or more organic complex parts, such as in the presence of ether or alcohol, make the water of cyanide-free slaine
The reactant aqueous solution of solution and metal cyanide salt prepares dmc catalyst, the metallic hydrogen oxidation of one or more of which alkalescence
Thing, metal carbonate and/or metal-oxide are present in the aqueous solution of the aqueous solution of cyanide-free slaine, metal cyanide salt
Or in both aqueous solutions, and metal hydroxides, metal carbonate and/or metal-oxide total of the alkalescence wherein used
Amount is 0.3 to 1.8 mol, preferably 0.6 to 1.6 mol, the alkali equivalent (use based on 1 mol of particularly preferred 0.8 to 1.4 mol
In the metal cyanide salt meter synthesizing this catalyst).
By at least one H-functional starter substance, at least one alkylene oxide and carbon dioxide system in the presence of dmc catalyst
The method of standby polyether carbonate polyol can continuously, semi-batch ground or carry out discontinuously.
According to the present invention obtain polyether carbonate polyol be generally of at least 1, preferably 2 to 8, particularly preferred 2 to 6 and
The degree of functionality of the most particularly preferred 2 to 4.Molecular weight is preferably 400 to 10,000 g/mol and particularly preferably 500 to 6000 g/
mol。
Generally, the alkylene oxide with 2 to 24 carbon atoms may be used for the method for the present invention.There are 2 to 24 carbon atoms
Alkylene oxide for example, selected from following one or more compounds: oxirane, expoxy propane, 1-epoxy butane, 2,3-rings
Oxygen butane, 2-methyl isophthalic acid, 2-expoxy propane (epoxy iso-butane), 1-epoxypentane, 2,3-epoxypentane, 2-methyl isophthalic acid, 2-ring
Oxygen butane, 3-methyl isophthalic acid, 2-epoxy butane, 1-oxepane, 2,3-oxepane, 3,4-oxepane, 2-methyl isophthalic acid, 2-ring
Oxygen pentane, 4-methyl isophthalic acid, 2-epoxypentane, 2-ethyl-1,2-epoxy butane, 1-oxepane, 1-octylene oxide, 1-epoxy nonyl
Alkane, 1-decamethylene, 1-epoxyundecyl, 1-Epoxydodecane, 4-methyl isophthalic acid, 2-epoxypentane, butadiene monoxide, an oxygen
Change isoprene, cyclopentene oxide, cyclohexene oxide, aoxidize cycloheptene, aoxidize cyclo-octene, styrene oxide, oxidation methyl benzene
Ethylene, pinene oxide, single or multiple epoxidized fat as glycerol list-, double-and three-ester, epoxidised fatty acid, epoxidation fat
The C of fat acid1-C24-ester, chloropropylene oxide, (+)-2,3-Epoxy-1-propanol and glycidyl derivatives, such as methyl glycidyl ether, ethyl shrinks sweet
Oil ether, 2-hexyl glycidyl ether, allyl glycidyl ether, glycidyl methacrylate, and epoxide-
Functional alkoxysilanes, such as 3-glycidyloxypropyl trimethoxy silane, 3-glycidyloxypropyl three second
TMOS, 3-glycidyloxypropyl tripropoxy silane, 3-glycidyloxypropyl methyl dimethoxy epoxide silicon
Alkane, 3-glycidyloxypropyl ethyl diethoxy silane, 3-glycidyloxypropyl three isopropoxy silane.Ring
Oxidative ethane and/or expoxy propane, particularly expoxy propane are preferably used as alkylene oxide.
Can serve as suitable H-functional starter substance has the chemical combination for alkoxylate with the H atom being activity
Thing.Active H atom and the group being active for alkoxylate are such as-OH ,-NH2(primary amine) ,-NH-(secondary amine) ,-SH
With-CO2H;-OH and-NH2It is preferred;-OH is particularly preferred.Such as having selected from following as H-functional starter substance
One or more compounds: single or multi-element alcohol, single or multi-element amine, multi-thiol, carboxylic acid, amino alcohol, amino carboxylic acid, mercaptan, hydroxyl
Base ester, polyether polyol, PEPA, polyesterether polyols, polyether carbonate polyol, polycarbonate polyol, poly-carbon
Acid esters, polymine, polyetheramine is (such as purchased from the so-called Jeffamine of Huntsman®, such as D-230, D-400, D-
2000, T-403, T-3000, T-5000 or the corresponding product purchased from BASF, such as polyetheramine D230, D400, D200, T403,
T5000), PolyTHF is (such as purchased from the PolyTHF of BASF®, such as PolyTHF®250,650S, 1000,1000S,
1400,1800,2000), PolyTHF amine (BASF product PolyTHF amine 1700), polyethers mercaptan, polyacrylate is many
Unit's alcohol, Oleum Ricini, the glycerol list of castor oil acid or diester, the monoglyceride of fatty acid, the glycerol of the chemical modification of fatty acid
Single-, double-and/or three-ester, and per molecule comprises the C of average at least 2 OH groups1-C24-alkyl fatty esters.Per molecule bag
C containing average at least 2 OH groups1-C24-alkyl fatty esters is such as commercial product, such as Lupranol Balance®
(BASF AG), Merginol®Type (Hobum Oleochemicals GmbH), Sovermol®Type (Cognis
Deutschland GmbH & Co. KG) and Soyol®TM type (USSC Co.).
Can serve as simple function initial substance has alcohol, amine, sulfur alcohol and carboxylic acid.Can serve as monofunctional alcohol has: methanol,
Ethanol, 1-propanol, 2-propanol, n-butyl alcohol, 2-butanol, the tert-butyl alcohol, 3-butene-1-ol, 3-butyne-1-ol, 2-methyl-3-fourth
Alkene-2-alcohol, 2-methyl-3-butyne-2-alcohol, propargyl alcohol, 2-methyl-2-propanol, 1-tert-butoxy-2-propanol, 1-amylalcohol, 2-penta
Alcohol, 3-amylalcohol, 1-hexanol, 2-hexanol, 3-hexanol, 1-heptanol, 2-enanthol, 3-enanthol, 1-capryl alcohol, sec-n-octyl alcohol, 3-capryl alcohol, 4-are pungent
Alcohol, phenol, 2-xenol, 3-xenol, 4-xenol, 2 hydroxy pyrimidine, 3-pyridone, 4-pyridone.Close
Suitable having as monofunctional amines: butylamine, tert-butylamine, amylamine, hexylamine, aniline, aziridine, pyrrolidine, piperidines, morpholine.Can
For use as having of simple function mercaptan: ethyl mercaptan, 1-propanethiol, 2-propanethiol, 1-butyl mercaptan, 3-methyl isophthalic acid-butyl mercaptan, 2-fourth
Alkene-1-mercaptan, thiophenol.It can be mentioned that having as monofunctional carboxylic: formic acid, acetic acid, propanoic acid, butanoic acid, fatty acid, such as
Stearic acid, Palmic acid, oleic acid, linoleic acid, linolenic acid, benzoic acid, acrylic acid.
Properly the polyhydric alcohol as H-functional starter substance be such as dihydroxylic alcohols (such as ethylene glycol, diethylene glycol, the third two
Alcohol, dipropylene glycol, 1,3-PD, BDO, Isosorbide-5-Nitrae-butylene glycol, Isosorbide-5-Nitrae-butynediols, neopentyl glycol, 1,5-penta 2
Alcohol, methyl pentanediol (such as 3-methyl isophthalic acid, 5-pentanediol), 1,6-hexanediol;1,8-ethohexadiol, decamethylene-glycol, 1,12-
Dodecanediol, double-(methylol) hexamethylene (such as Isosorbide-5-Nitrae-bis--(methylol) hexamethylene), 2,2'-ethylenedioxybis(ethanol)., tetraethylene glycol (TEG), poly-second two
Alcohol, dipropylene glycol, tripropylene glycol, polypropylene glycol, dibutylene glycol and polytetramethylene glycol);Trihydroxylic alcohol (such as trimethylolpropane, sweet
Oil, trihydroxy ethyl isocyanurate, Oleum Ricini);Tetrahydroxylic alcohol (such as tetramethylolmethane);Polyhydric alcohol (such as Sorbitol, hexose
Alcohol, sucrose, starch, starch hydrolysate, cellulose, cellulosic hydrolysates, the oil of hydroxyl-functional and fat, particularly castor
Oleum Sesami), and all modified products of above-mentioned alcohol and different amounts of 6-caprolactone.
H-functional starter substance is alternatively the material classification selected from polyether polyol, and particularly molecular weight Mn is 100 to 4,
Those of 000 g/mol.The polyether polyol being preferably made up of oxirane and propylene oxide repeat units, preferably have 35 to
The propylene oxide units content of 100%, particularly preferably has the propylene oxide units content of 50 to 100%.These can be epoxy
Ethane and the random copolymer of expoxy propane, gradient copolymer, replace or block copolymer.By expoxy propane and/or epoxy second
The suitable polyether polyol that alkane repetitive is constituted is such as Desmophen®、Acclaim®、Arcol®、Baycoll®、
Bayfill®、Bayflex®、Baygal®、PET®With the polyether polyol purchased from Bayer MaterialScience AG (such as
Desmophen® 3600Z、Desmophen® 1900U、Acclaim® Polyol 2200、Acclaim® Polyol 4000I、
Arcol® Polyol 1004、Arcol® Polyol 1010、Arcol® Polyol 1030、Arcol® Polyol 1070、
Baycoll® BD 1110、Bayfill® VPPU 0789、Baygal® K55、PET® 1004、Polyether®S180).Its
Its suitable homopolymerization poly(ethylene oxide) is such as to be purchased from the Pluriol of BASF SE®E trade mark, suitable homopolymerization poly(propylene oxide)
For such as purchased from the Pluriol of BASF SE®P brand, the mixed copolymer of suitable oxirane and expoxy propane is such as
Pluronic purchased from BASF SE®PE or Pluriol®RPE trade mark.
H-functional starter substance is alternatively the material classification selected from PEPA, and particularly molecular weight Mn is 200 to 4,
Those of 500 g/mol.The most dual functional polyester is used as PEPA.PEPA is preferably by acid alternately and alcohol list
Unit is constituted.Can serve as acid constituents has such as succinic acid, maleic acid, maleic anhydride, adipic acid, phthalic anhydride, adjacent benzene
Dioctyl phthalate, M-phthalic acid, p-phthalic acid, tetrahydrophthalic acid, tetrabydrophthalic anhydride, hexahydrophthalic anhydride
Or above-mentioned acid and/or the mixture of anhydride.Such as ethylene glycol, 1,2-propylene glycol, 1,3-propylene glycol, 1,4-is had as alkoxide component
Butanediol, 1,5-pentanediol, neopentyl glycol, 1,6-HD, 1,4-be double-(methylol)-hexamethylene, diethylene glycol, dipropyl two
Alcohol, trimethylolpropane, glycerol, tetramethylolmethane or the mixture of above-mentioned alcohol.If binary or polynary polyether polyol are used as
Alkoxide component, then obtain polyesterether polyols, its initial substance being also used as preparing polyether carbonate polyol.Preferably,
The polyether polyol using Mn=150 to 2000 g/mol is used for preparing polyesterether polyols.
It is 150 to 4500 g/mol that PCDL is also used as H-functional starter substance, particularly molecular weight Mn,
Being preferably the PCDL of 500 to 2,500, it is such as by making phosgene, dimethyl carbonate, diethyl carbonate or carbonic acid two
Phenyl ester and difunctional alcohol or PEPA or polyether polyol reaction preparation.The example of Merlon is such as at EP-A
Find in 1359177.Such as can serve as PCDL has purchased from Bayer MaterialScience AG's
Desmophen®C-type, such as Desmophen®C 1100 or Desmophen® C 2200。
In another embodiment of the present invention, polyether carbonate polyol can serve as H-functional starter substance.Special
, the polyether carbonate polyol that can be obtained is not used by the method for the present invention described herein.As H-functional initiator
These polyether carbonate polyols of matter are prepared in advance in single reactions steps.
H-functional starter substance is generally of 1 to 8, and (i.e. per molecule is the H of activity for polymerization to the degree of functionality of preferably 2 or 3
Atomic number).H-functional starter substance individually or uses with the form of the mixture of at least two H-functional starter substance.
Preferably H-functional starter substance is the alcohol of logical formula (II)
HO-(CH2)x-OH (II)
Wherein x is the number of 1 to 20, the even number of preferably 2 to 20.The example of the alcohol according to formula (II) is ethylene glycol, 1,4-
Butanediol, 1,6-HD, 1,8-ethohexadiol, 1,10-decanediol and 1,12-dodecanediol.Other preferred H-official can rise
Beginning material is neopentyl glycol, trimethylolpropane, glycerol, tetramethylolmethane, produces with the reaction of 6-caprolactone according to the alcohol of formula (II)
The product of thing, such as trimethylolpropane and 6-caprolactone, the product of glycerol and 6-caprolactone and tetramethylolmethane with
The product of 6-caprolactone.Other is diethylene glycol preferably as H-functional starter substance, dipropylene glycol, Oleum Ricini, mountain
Pears sugar alcohol, and the polyether polyol being made up of polyalkylene oxide repeat units.
It is particularly preferred that H-functional starter substance is selected from one or more following compounds: ethylene glycol, 1,2-the third two
Alcohol, 1,3-PD, 1,3 butylene glycol, BDO, 1,5-PD, 2-methyl isophthalic acid, ammediol, neopentyl glycol, 1,
6-hexanediol, 1,8-ethohexadiol, diethylene glycol, dipropylene glycol, glycerol, trimethylolpropane, double and three-functional polyethers is polynary
Alcohol, by double or three-H-functional starter substances and expoxy propane or double or three-H-functional starter substances, expoxy propane and oxidation
The polyether polyol that ethylene is formed.Polyether polyol preferably has the sense of the molecular weight Mn and 2 to 3 of 62 to 4,500 g/mol
Degree, the degree of functionality of the molecular weight Mn and 2 to 3 of particularly 62 to 3,000 g/mol.
By polynary by preparing polyether carbonate on carbon dioxide and alkylene oxide catalytic addition to H-functional starter substance
Alcohol.Within the scope of the present invention, " H-official can " be interpreted as that per molecule initial substance is for H atom number that alkoxylate is activity.
Dmc catalyst in principle by known in the art (see for example US-A 3 404 109, US-A 3 829 505,
US-A 3 941 849 and US-A 5 158 922).US-A 5 470 813、EP-A 700 949、EP-A 743 093、EP-A
761 708, the dmc catalyst described in WO 97/40086, WO 98/16310 and WO 00/47649 is in the homopolymerization of epoxide
In there is the highest activity, it is allowed to prepare polyether polyol with extremely low catalyst concn (25 ppm or lower) so that generally
It is no longer necessary to separating catalyst from final products.Representative instance is the high activity dmc catalyst described in EP-A 700 949,
In addition to bimetallic cyaniding compounds (such as six cyanogen cobalt (III) acid zinc) and organic complex part (the such as tert-butyl alcohol),
It also comprises the number-average molecular weight polyethers more than 500 g/mol.
The preparation of alkalescence dmc catalyst is disclosed in US 5 783 513.Described invention provides based on being used for preparing
The slaine quality of catalyst, as the form of metal-oxide, basicity is the dmc catalyst of 0.2 to about 2.0 weight %.These
The most amorphous catalyst produces the viscosity of improvement and lower degree of unsaturation being prepared by alkylene oxide in polyether polyol.Should
Therefore catalyst is only used for the homopolymerization of expoxy propane.The document the copolymerization of not mentioned use carbon dioxide.
US 6 716 788 B2 is disclosed in amount based on the slaine used, the alkali metal compound of 0.03 to 0.4 mol
Preparation alkalescence dmc catalyst, described alkali metal compound and metal cyanides in the presence of (adding oxide and/or hydroxide)
Reactant salt.The homopolymerization of thus prepared dmc catalyst epoxide in the presence of not having carbon dioxide.Do not mention use
The copolymerization of carbon dioxide.
The dmc catalyst of the present invention is preferably by following acquisition
I () in the first step, in the presence of one or more organic complex parts, such as, in the presence of ether or alcohol, makes
The aqueous solution of cyanide-free slaine and the reactant aqueous solution of metal cyanide salt, the metal hydrogen-oxygen of one or more of which alkalescence
Compound, metal carbonate and/or metal-oxide be present in the aqueous solution of cyanide-free slaine, metal cyanide salt water-soluble
In liquid or both aqueous solutions, and metal hydroxides, metal carbonate and/or the metal-oxide of the alkalescence wherein used
Amount is 0.3 to 1.8 mol, preferably 0.6 to 1.6 mol, the alkali equivalent (use based on 1 mol of particularly preferred 0.8 to 1.4 mol
In the metal cyanide salt meter synthesizing this catalyst),
(ii) wherein in second step, divided from the suspension that (i) obtains by known technology (such as centrifugal or filtration)
From solid,
(iii) wherein the most in the third step, with the solid of the solution washing separation of organic complex part (such as
By settling flux, then by filtering or centrifugal separation again),
(iv) wherein optionally the most after the pulverizing, subsequently at the temperature of usual 20 to 120 DEG C and usual 0.1 mbar to normal pressure
The solid obtained it is dried under the pressure of (1013 mbar),
The most in the first step or and then, after precipitation bimetallic cyaniding compounds (second step), one is added
Or multiple organic complex part, preferably excess (based on bimetallic cyaniding compounds), and optionally other complex formation group
Point.
The bimetallic cyaniding compounds comprised in the dmc catalyst of the present invention is water solublity cyanide-free slaine and water
The product of solube metallic cyanide salt, wherein for preparing the cyanide-free slaine of dmc catalyst, metal cyanide salt
Or above-mentioned both salt comprises the alkalescence of 0.3 to 1.8 mol, preferably 0.6 to 1.6 mol, particularly preferred 0.8 to 1.4 mol
(based on 1 mol being used for synthesizes this catalysis to the alkali equivalent of metal hydroxides, metal carbonate and/or metal oxide form
The metal cyanide salt meter of agent).
Such as, by aqueous solution and six cyanogen of zinc chloride (preferably with respect to metal cyanide salt such as Cobalt Potassium Cyanide excess)
Cobalt acid potassium mix, then in gained suspension add dimethoxy-ethane (glyme) or the tert-butyl alcohol (preferably with respect to
Hexacyanocobaltate acid zinc overdose), the Cobalt Potassium Cyanide wherein used the most in advance with 0.3 to 1.8 mol, preferably 0.6 to 1.6 mol,
The alkalescence of particularly preferred 0.8 to 1.4 mol alkali equivalent (based on 1 mol based on the metal cyanide salt synthesizing this catalyst)
Metal hydroxides, metal carbonate and/or metal-oxide mixing.
The cyanide-free slaine being suitable for preparing bimetallic cyaniding compounds preferably has logical formula (III)
M(X)n (III)
Wherein
M is selected from metal cation Zn2+, Fe2+, Ni2+, Mn2+, Co2+, Sr2+, Sn2+, Pb2+And Cu2+, M is preferably Zn2+, Fe2 +, Co2+Or Ni2+,
X is one or more (the most different) aniones, be preferably selected from halogen ion (i.e. fluorion, chloride ion, bromine from
Son, iodide ion), hydroxyl, sulfate radical, carbonate, cyanate radical, thiocyanate radical, isocyano, isosulfocyanate radical, carboxylate radical, grass
Acid group and the anion of nitrate anion;
When X=sulfate radical, carbonate or oxalate, n is 1, and
When X=halogen ion, hydroxyl, cyanate radical, thiocyanate radical, isocyano, when isosulfocyanate radical or nitrate anion, n is 2,
Or suitably cyanide-free slaine has logical formula (IV)
Mr(X)3 (IV)
Wherein
M is selected from metal cation Fe3+, Al3+And Cr3+,
X is one or more (the most different) aniones, be preferably selected from halogen ion (i.e. fluorion, chloride ion, bromine from
Son, iodide ion), hydroxyl, sulfate radical, carbonate, cyanate radical, thiocyanate radical, isocyano, isosulfocyanate radical, carboxylate radical, grass
Acid group and the anion of nitrate anion;
When X=sulfate radical, carbonate or oxalate, r is 2, and
When X=halogen ion, hydroxyl, cyanate radical, thiocyanate radical, isocyano, isosulfocyanate radical, carboxylate radical or nitrate anion
Time, r is 1,
Or the slaine of suitable cyanide-free has logical formula V
M(X)s (V)
Wherein
M is selected from metal cation Mo4+, V4+And W4+,
X is one or more (the most different) aniones, be preferably selected from halogen (i.e. fluorion, chloride ion, bromide ion,
Iodide ion), hydroxyl, sulfate radical, carbonate, cyanate radical, thiocyanate radical, isocyano, isosulfocyanate radical, carbonyl acid group, oxalic acid
Root and the anion of nitrate anion;
When X=sulfate radical, carbonate or oxalate, s is 2, and
When X=halogen ion, hydroxyl, cyanate radical, thiocyanate radical, isocyano, isosulfocyanate radical, carboxylate radical or nitrate anion
Time, s is 4,
Or suitably cyanide-free slaine has logical formula (VI)
M(X)t (VI)
Wherein
M is selected from metal cation Mo6+And W6+,
X is one or more (the most different) aniones, be preferably selected from halogen ion (i.e. fluorion, chloride ion, bromine from
Son, iodide ion), hydroxyl, sulfate radical, carbonate, cyanate radical, thiocyanate radical, isocyano, isosulfocyanate radical, carboxylate radical, grass
Acid group and the anion of nitrate anion;
When X=sulfate radical, carbonate or oxalate, t is 3, and
When X=halide ion, hydroxyl, cyanate radical, thiocyanate radical, isocyano, isosulfocyanate radical, carboxylate radical or nitric acid
During root, t is 6.
Suitably the example of cyanide-free slaine is zinc chloride, zinc bromide, zinc iodide, zinc acetate, acetopyruvic acid zinc,
Zinc dibenzoate., zinc nitrate, iron sulfate (II), ferric bromide (II), iron chloride (II), cobaltous chloride (II), Cobaltous rhodanide (II), chlorination
Nickel (II) and nickel nitrate (II).The mixture of different metal salt can also be used.
The metal cyanide salt being suitable for preparing bimetallic cyaniding compounds preferably has logical formula (VII)
(Y)a M'(CN)b (A)c (VII)
Wherein
M' is selected from one or more following metal cations: Fe (II), Fe (III), Co (II), Co (III), Cr
(II), Cr (III), Mn (II), Mn (III), Ir (III), Ni (II), Rh (III), Ru (II), V (IV) and V (V), M' is preferred
For selected from one or more following metal cations: Co (II), Co (III), Fe (II), Fe (III), Cr (III), Ir
(III) and Ni (II),
Y is selected from one or more following metal cations: alkali metal (i.e. Li+, Na+, K+, Rb+, Cs+) and alkaline earth gold
Belong to (i.e. Be2+, Ca2+, Mg2+, Sr2+, Ba2+),
A is selected from one or more following aniones: halogen ion (i.e. fluorion, chloride ion, bromide ion, iodide ion),
Hydroxyl, sulfate radical, carbonate, cyanate radical, thiocyanate radical, isocyano, isosulfocyanate radical, carboxylate radical, oxalate or nitric acid
Root, and
A, b and c are integer, so select the value of a, b and c so that produce the electric neutrality of metal cyanide salt;A is preferably
1,2,3 or 4;B is preferably 4,5 or 6;C preferably has value 0.
The suitably example of metal cyanide salt is six cyanogen cobalt (III) acid potassium, six cyanogen ferrum (II) acid potassium, six cyanogen ferrum (III)
Acid potassium, six cyanogen cobalt (III) acid calcium and six cyanogen cobalts (III) acid lithium.
The preferred bimetallic cyaniding compounds comprised in the dmc catalyst of the present invention is the compound of logical formula (VIII)
Mx[M’x,(CN)y]z (VIII)
Wherein M is if formula (III) is to defined in (VI), and
M' as defined in formula (VII), and
X, x', y and z are integer and are selected so that produce the electric neutrality of bimetallic cyaniding compounds.
Preferably,
X=3, x '=1, y=6 and z=2,
M=Zn (II), Fe (II), Co (II) or Ni (II), and
M '=Co (III), Fe (III), Cr (III) or Ir (III).
The suitably example of bimetallic halide compound a) is six cyanogen cobalt (III) acid zinc, six cyanogen iridium acid (III) zinc, six
Cyanogen ferrum (III) acid zinc and six cyanogen cobalts (III) acid cobalt (II).Suitably other example of bimetallic cyaniding compounds is such as at US
5 158 922 (8 hurdles, 29-66 row) find.Six cyanogen cobalt (III) acid zinc are particularly preferably to use.
It is preferably unit for preparing the hydroxide of the alkalinous metal of the dmc catalyst of the present invention, carbonate and oxide
The metal of 1a and the 2a race of element periodic chart (see for example " Handbook of Chemistry and Physics, the 63rd edition ")
Oxide or hydroxide.Suitably the example of the hydroxide of alkalinous metal, metal-oxide and metal carbonate is carbon
Acid sodium, sodium hydroxide, potassium carbonate, potassium hydroxide, calcium oxide, calcium hydroxide, barium hydroxide or Barium monoxide.
Prepare the organic complex part added in dmc catalyst such as US 5 158 922 (referring particularly to 6 hurdles, 9
To 65 row), US 3 404 109, US 3 829 505, US 3 941 849, EP-A 700 949, EP-A 761 708, JP 4
Disclosed in 145 123, US 5 470 813, EP-A 743 093 and WO-A 97/40086.Such as, join as organic complex
Body have the heteroatomic water-soluble organic compounds with such as oxygen, nitrogen, phosphorus or sulfur, it can be with double metal cyanide chemical combination
Thing forms complex.Preferably organic complex part is alcohol, aldehyde, ketone, ether, ester, amide, urea, nitrile, thioether and mixture thereof.
Particularly preferred organic complex part is aliphatic ether (such as dimethoxy-ethane), water-soluble aliphatic alcohol (such as ethanol, isopropyl
Alcohol, n-butyl alcohol, isobutanol, sec-butyl alcohol, the tert-butyl alcohol, 2-M3BOL and 2-methyl-3-butyne-2-alcohol), comprise fat
The compound of race or alicyclic ether and aliphatic hydroxide radical (such as ethylene glycol mono-tert-butyl ether, diethylene glycol list tertbutyl ether,
Tripropylene glycol monomethyl ether and 3-methyl-3-oxetanes (oxetan)-methanol).Most preferably organic complex part choosing
From one or more of compound: dimethoxy-ethane, the tert-butyl alcohol, 2-M3BOL, 2-methyl-3-butine-
2-alcohol, ethylene glycol mono-tert-butyl ether and 3-methyl-3-oxetanes (oxetan)-methanol.
In the dmc catalyst of the preparation present invention, optionally employ following compounds one or more complex shapes other
One-tenth component: polyethers, polyester, Merlon, poly alkylene glycol sorbitan ester, poly alkylene glycol glycidyl ether,
Polyacrylamide, poly-(acrylamide-co-acrylic acid), polyacrylic acid, poly-(acrylic acid-co-maleic acid), polyacrylonitrile, poly-third
Olefin(e) acid Arrcostab, polyalkyl methacrylate, polyvinylmethyl ethers, polyvinyl ethyl ether, polyvinyl acetate, polyethylene
Alcohol, poly N-vinyl pyrrolidone, poly-(NVP-co-acrylic acid), and polyvinyl methyl ketone, poly-(4-ethylene
Base phenol), poly-(acrylic acid-co-styrene), oxazoline polymer, polyalkyleneimine, maleic acid and maleic anhydride
Thing, hydroxyethyl cellulose and polyacetals, or glycidyl ether, glycosides, the carboxylate of polyhydric alcohol, gallic acid or salt, its ester or acyl
Amine, cyclodextrin, phosphorus compound, α, beta-unsaturated carboxylic acid ester or ion surface or interfacial agent.
Preferably, in the dmc catalyst of the preparation present invention, in the first step, in organic complex part (the most tertiary fourth
Alcohol) in the presence of, make based on metal cyanide salt, slaine (the such as chlorination that stoichiometric excess (at least 50 mol%) uses
Zinc) aqueous solution, i.e. cyanide-free slaine is 2.25:1.00 to the molar ratio of metal cyanide salt, with metal cyanides
The reactant aqueous solution of salt (such as Cobalt Potassium Cyanide), one or more of which alkalescence metal hydroxides, metal carbonate and/
Or metal-oxide is present in the aqueous solution of cyanide-free slaine, the aqueous solution of metal cyanide salt or both aqueous solutions
In so that formed and comprise bimetallic cyaniding compounds (such as zinc hexacyanocobaltate), water, excess cyanide-free slaine and organic
The suspension of complex ligands.
Organic complex part may reside in the aqueous solution of cyanide-free slaine and/or metal cyanide salt, or
It is added directly in the suspension obtained after precipitation bimetallic cyaniding compounds.Having been found that advantageously will be without cyanogen
The aqueous solution of compound slaine stirs with the aqueous solution of metal cyanide salt and organic complex part accompanied by intense and is mixed
Closing, metal hydroxides, metal carbonate and/or the metal-oxide of one or more of which alkalescence is present in cyanide-free gold
Belong in the aqueous solution of salt, the aqueous solution of metal cyanide salt or both aqueous solutions.Optionally, then by another kind of complex shape
The suspension formed in the divisional processing first step in groups.Complex formed component preferably with water and the mixing of organic complex part
The form of thing uses.The method for optimizing carrying out the first step (i.e. supending) uses mixing nozzle, particularly preferably uses WO-A
Injection disperser described in 01/39883 is carried out.
In second step, by known technology, such as centrifugal or filtration, by solid (i.e. the precursor of the catalyst of the present invention)
Separate from suspension.
In preferred modification, in the 3rd method step, divide with the solution washing of organic complex part subsequently
From solid (such as by settling flux with subsequently by filtering or centrifugal separation again).In such a way, for example, it is possible to from
The catalyst of the present invention is removed aqueous by-product, such as potassium chloride.Preferably, the organic complex in aqueous cleaning solution
The amount of part is 40 to 80 weight %, based on complete soln.
Optionally, it is preferably based on complete soln, another so that 0.5 to 5 weight % aqueous cleaning solution in the 3rd step to add
A kind of complex forms component.
Wash the solid of separation the most more than once.Preferably, use in first washing step (iii-1)
The solution washing (such as by settling flux, then by filtering or centrifugal separation again) of unsaturated alcohol, in order to thus from this
The catalyst of invention removes such as aqueous by-product, such as potassium chloride.It is particularly preferred that the insatiable hunger in aqueous cleaning solution
It is 40 to 80 weight % with the amount of alcohol, complete soln based on first washing step.In another washing step (iii-2),
First washing step is repeated once or several times, preferably one to three time, or preferably non-aqueous solution, such as organic complex is joined
Body and another kind of complex form the mixture of component or solution, and (preferably 0.5 to 5 weight % based on step (iii-2) is washed
Wash the total amount of solution) it is used as wash solution, and solid be washed once or several times, preferably one to three time.
Then optionally the most after the pulverizing, at the temperature of usual 20 to 100 DEG C and usual 0.1 mbar to normal pressure (1013
Mbar) it is dried separating the solid with optionally washing under pressure.
For by filtering the dmc catalyst separating the present invention from suspension, wash filter cake and the method for optimizing being dried
Described in WO-A 01/80994.
The present invention also provide for a kind of in the presence of at least one dmc catalyst by one or more H-functional starter substances,
One or more alkylene oxides and carbon dioxide prepare the method for polyether carbonate polyol, wherein for preparing dmc catalyst
Cyanide-free slaine, metal cyanide salt or above-mentioned both salt comprise 0.3 to 1.8 mol, preferably 0.6 to 1.6 mol, special
The metallic hydrogen of the alkalescence of the most preferably 0.8 to 1.4 mol (based on 1 mol based on the metal cyanide salt synthesizing this catalyst)
The alkali equivalent of oxide, metal carbonate and/or metal oxide form, and wherein
(α) by H-functional starter substance, or the mixture of at least two H-functional starter substance is pre-filled with, and optionally
Water and/or other effumability compound (" being dried ") is removed by heating up and/or reducing pressure, before or after being wherein dried, to
H-functional starter substance, or the mixture of at least two H-functional starter substance are added dmc catalyst,
(β) for activation
(β 1), in first activation step, adds one or more alkylene oxides in the mixture coming from step (α)
Part I amount (total amount based on the alkylene oxide amount used in activation and copolymerization), this interpolation of the partial amount of its alkylene oxide
Can be optionally at CO2In the presence of carry out, but preferably there is no CO2In the presence of carry out, and the most in either case etc.
Treat until temperature peak (" focus ") occurring due to follow-up heat-producing chemical reaction, and/or reactor occurs pressure drop,
(β 2) is in second activation step, after activation step previously reaches temperature peak, previous to coming from
The mixture of activation step adds the Part II amount of one or more alkylene oxides (based on the epoxy used in activation and copolymerization
The total amount of alkane amount), this interpolation of the partial amount of its alkylene oxide can be optionally at CO2In the presence of carry out, but preferably do not having
There is CO2In the presence of carry out, and wait until, due to follow-up heat-producing chemical reaction, temperature occurs the most in either case
Degree peak value (" focus "), and/or reactor occurs pressure drop,
(β 3), optionally in the 3rd activation step or another activation step, reaches temperature in activation step previously
Degree peak value after, by step (β 2) repeat zero to five time, preferably one to four time, the most once, its alkylene oxide
This interpolation of partial amount or these be added on and there is no CO2In the presence of carry out, and wait until the most in either case
Due to follow-up heat-producing chemical reaction, temperature peak (" focus ") occurs, and/or reactor occurs pressure drop,
(β 4) is optional in another or multiple activation step, after activation step previously reaches temperature peak,
Step (β 3) is repeated one to five time, preferably one to four time, the most once, this of the partial amount of its alkylene oxide
Add or these are added on CO2In the presence of carry out, and wait until the most in either case due to follow-up heat release
Learn reaction and temperature peak (" focus ") occur, and/or reactor occurs pressure drop,
(γ) one or more alkylene oxides and carbon dioxide are continuously metered in the mixture coming from step (β) (" altogether
Poly-").Alkylene oxide for copolymerization can be identical or different with the alkylene oxide for activation.
In preferred embodiments, the portion of one or more alkylene oxides each used in the activation in step β 1 to β 4
Component is 2.0 to 15.0 weight %, preferably 2.5 to 14.0 weight %, and particularly preferably 3.0 to 13.0 weight % are (based on activation
Total amount with the alkylene oxide amount used in copolymerization).
Step (α):
In order to pass through alkylene oxide (epoxide) and carbon dioxide catalytic addition in the presence of the dmc catalyst of the present invention
Polyether carbonate polyol is prepared to H-functional starter substance (starting material), by H-functional starter substance, or at least two H-
The mixture of functional starter substance is pre-filled with.Optionally in step (α)
(α 1) is by H-functional starter substance, or the mixture of at least two H-functional starter substance is pre-filled with, and
(α 2) makes the temperature of initial substance or mixture reach 50 to 200 DEG C, preferably 80 to 160 DEG C, particularly preferred 100 to
140 DEG C, and/or the pressure in reactor is dropped below 500 mbar, preferably 5 mbar to 100 mbar.Can also be by
Nitrogen stream passes through reactor.
Dmc catalyst can preexist in H-functional starter substance, or preexist at least two H-official and can rise
In the mixture of beginning material, but also can be the most just to H-functional starter substance or the mixture of H-functional starter substance
The dmc catalyst of middle interpolation drying.Dmc catalyst can add with solid-state, or with the suspension in H-functional starter substance
The form of liquid is added.If catalyst adds with the form of suspension, it joins one or more H-the most before the drying
In functional starter substance.
Step (β):
The metering of one or more alkylene oxides and optional carbon dioxide is added on dry initial substance or multiple initial substance
Mixture after and carry out adding after dmc catalyst, described dmc catalyst is before or after dry initial substance
Add with the form of solid or suspension.If dmc catalyst adds after dry initial substance, then dmc catalyst Ying You
Choosing is such as dried in the method similar with dry initial substance.Interpolation one can be measured in principle by different way
Or multiple alkylene oxide and carbon dioxide.Can vacuum or the first pressure being pre-selected start metering add.Preferably by means of logical
Entering the noble gas of such as nitrogen to produce first pressing, pressure (definitely) is set as 10 mbar to 10 bar, preferably 100 mbar
To 8 bar and more preferably 500 mbar to 6 bar.In a kind of particularly preferred embodiment, come from the one of step (α)
Or the mixture of multiple initial substance and dmc catalyst stands 1.5 bar to 10 bar at a temperature of 100 DEG C to 130 DEG C
(definitely), the inert gas pressure (nitrogen or rare gas, such as argon) of particularly preferred 3 bar to 6 bar (definitely) is at least
Once, preferably three times, and the most at once within the period of at most 15 minutes, in every case overvoltage is reduced to 1 bar
(definitely).It addition, in a same particularly preferred embodiment, by noble gas (nitrogen or rare gas, such as argon
Gas) it is passed through at a temperature of 40 DEG C to 150 DEG C and comes from one or more initiator compounds of step (α) and dmc catalyst
Mixture, and at the same time, apply the decompression of 10 mbar to 800 mbar, particularly preferred 50 mbar to 200 mbar (absolutely
Right).
Step (γ):
One or more alkylene oxides and carbon dioxide can measure interpolation simultaneously or sequentially, and the whole amount of carbon dioxide is permissible
Once add, or metering adds during the response time.Carbon dioxide preferably measures interpolation.The meter of one or more alkylene oxides
The metering interpolation that amount is added with carbon dioxide is carried out simultaneously or sequentially.If using multiple in synthesizing polyether carbonate polyol
Alkylene oxide, then its metering interpolation can be added by metering respectively or add to enter simultaneously or sequentially by one or more meterings
OK, at least two alkylene oxide measures interpolation as a mixture.Added by the metering of alkylene oxide and carbon dioxide, Ke Yihe
Become random, alternately, block-wise or gradient shape polyether carbonate polyol.Alkylene oxide free during reaction in reactant mixture
Concentration is preferably > 0 to 40 weight %, particularly preferably > 0 to 25 weight %, and most preferably > 0 to 15 weight % is (in each situation
Under weight based on reactant mixture).
It is preferably based on the amount of calculation of the carbon dioxide introducing polyether carbonate polyol, uses the carbon dioxide of excess,
Because carbon dioxide reaction is slow, the carbon dioxide of excess is favourable.The amount of carbon dioxide can pass through described reaction condition
Under gross pressure determine.As the gross pressure (definitely) of the copolymerization preparing polyether carbonate polyol, 0.01 to 120 bar,
Preferably 0.1 to 110 bar, particularly preferred 1 to 100 bar has proven to favourable.For the method according to the invention, in addition
Have shown that the copolymerization preparing polyether carbonate polyol advantageously at 50 to 150 DEG C, preferably 60 to 145 DEG C, particularly preferred 70
Carry out to 140 DEG C and the most particularly preferred 110 to 120 DEG C.If being set lower than the temperature of 50 DEG C, then react stopping.It is being higher than
At a temperature of 150 DEG C, it is not desirable to have the amount of by-product significantly increase.It is further noted that CO2At the temperature and pressure selected
Under be changed into liquid and/or supercritical fluid from gaseous state as far as possible.But, CO2Reactor can also be joined in solid form
In, then under the reaction condition selected, it is transformed into liquid and/or supercritical fluid.
Particularly preferred reactor is: tubular reactor, stirred tank and loop reactor.Polyether polycarbonate polyhydric alcohol can
To prepare in stirred tank, according to embodiment and mode of operation, this stirred tank passes through reactor jacket, internal cooling surface
And/or the cooling surface being positioned at pump loop is cooled down.For security reasons, the free epoxy in the reactant mixture of stirred tank
The content of compound is not to be exceeded that 15 weight % (see for example WO-A 2004/081082;Page 3;14 row).Therefore should be specifically noted that
Wherein it was not to move out in the semi-batch operation of product before reaction terminates, and the ring being wherein continuously removed in the work continuously of product
The metering rate of oxide.Should so regulate the metering rate of epoxide so that despite the presence of the inhibitory action of carbon dioxide,
Epoxide reacts the most rapidly.Can continuously or non-continuously supply carbon dioxide.Whether this depends on epoxide
Sufficiently rapidly consume, and whether product intends to comprise optionally without CO2Polyether block.Amount (the shape with pressure of carbon dioxide
Formula represents) can also change during epoxide adds.The CO added during epoxide can be gradually increased2Pressure, or
Reduce this pressure or keep this pressure constant.
Copolymerization (in the stirred tank of step (γ) another may embodiment be characterised by during reaction by one or
Multiple H-functional initiator compound is continuously metered in reactor.H-official during continuous metering enters reactor in course of reaction
The amount of energy initiator compound is preferably at least 20 mol% equivalents, and particularly preferably 70 to 95 mol% equivalents are (in every case
Total amount based on H-functional initiator compound).
Catalyst/the initiator mixture of activation can in stirred tank or different reaction vessel (tubular reactor or
Loop reactor) in epoxide and carbon dioxide (further) copolymerization.
In the case of tubular reactor, by continuous to the catalyst of activation and starting material and epoxide and carbon dioxide
Pump by pipe.The molar ratio of reaction partner (Reaktionspartner) changes according to required polymer.At one
In preferred embodiment, carbon dioxide adds with its supercritical form, the metering of the most quasi-liquid form, to allow the mixed of each component
Dissolubility is more preferable.In order to preferably be thoroughly mixed each reaction partner, it is advantageously embedded such as by Ehrfeld
The hybrid element that Mikrotechnik BTS GmbH sells, or improve the blender-heat exchanger unit of mixing and thermal losses simultaneously
Part.
Even loop reactor may be used for preparing polyether polycarbonate polyhydric alcohol.Generally, these include utilizing material to follow
The reactor of ring, such as spray circuits reactor, it can also work continuously, or the loop of tubular reactor.Use back
Road reactor is particularly advantageous, because can carry out backmixing wherein so that epoxide concentration will be low.In order to
Realize converting completely, pipe (" resident pipe (Verweilrohr) ") is often provided in downstream.
Can have low by-products content by the polyether carbonate polyol that the method for the present invention obtains, can have no to be stranded
Difficult ground, reacts especially by with two-and/or polyisocyanates, and processing produces polyurethane, particularly flexible polyurethane foam.
Polyurethane is applied, polyether carbonate of based on H-functional initiator compound that degree of functionality be at least 2 is preferably used polynary
Alcohol.Such as detergent and cleaning agent can be may be used in addition by the polyether carbonate polyol that the method for the present invention obtains to prepare
The process chemical that material, drilling fluid, fuel additive, ion and nonionic surfactant, lubricant, papermaking or fabric produce
Or the application of cosmetic formulations material.Well known by persons skilled in the art is according to described application, the polyether carbonate of use
Polyhydric alcohol must is fulfilled for specific material property, such as molecular weight, viscosity, polydispersity, degree of functionality and/or hydroxyl value
(Hydroxylzahl).
Embodiment
Weight average molecular weight and the number-average molecular weight of resulting polymers measure by means of gel permeation chromatography (GPC).Step
According to DIN 55672-1: " Gelpermeationschromatographie(gel permeation chromatography), part 1-
Tetrahydrofuran als Elutionsmittel (oxolane is as eluant) ".The polystyrene of known molecular amount
Sample is used for calibrating.
Measure OH value (hydroxyl value) according to DIN 53240-2, but be that instead of THF/ dichloromethane, pyridine is used as solvent.With
The KOH ethanol solution of 0.5 molar concentration carries out titrating (by means of potentiometry identification terminal).Have by the hydroxyl of certificate validation
The Oleum Ricini of value is used as test substances.The unit indicated with " mg/g " represents mg [KOH]/g [polyether carbonate polyol].
By means of1H-NMR (Bruker, DPX 400,400 MHz;Pulse protocol zg30, waiting time d1:10 s, 64
Secondary scanning) measure the CO introduced in final polyether carbonate polyol2Amount and propylene carbonate to polyether carbonate
The ratio of polyhydric alcohol.In every case sample is dissolved in the chloroform of deuterate.1Important resonance in H-NMR is (based on TMS
=0 ppm) as follows:
Cyclic carbonate (being formed as by-product) resonates at 4.5 ppm, is derived from and is incorporated in polyether carbonate polyol
Carbon dioxide carbonic ester (5.1 to 4.8 ppm resonate), unreacted PO resonates at 2.4 ppm, and polyether polyol is (i.e.
Carbon dioxide without introducing) to resonate at 1.2 to 1.0 ppm, 1 introduced as starter molecules, 8-ethohexadiol is 1.6 to 1.52
Ppm resonates.
The mole introducing the carbonic ester in polymer in reactant mixture calculates according to equation below (IX), wherein uses
Below abbreviation:
Resonance area (corresponding to H atom) under 4.5 ppm of F (4.5)=cyclic carbonate
The resonance under 5.1-4.8 ppm of the H atom of F (5.1-4.8)=polyether carbonate polyol and cyclic carbonate
Area
The unreacted PO of F (2.4)=free is at the resonance area of 2.4 ppm
F (1.2-1.0)=polyether polyol is at the resonance area of 1.2-1.0 ppm
F (1.6-1.52)=1,8-ethohexadiol (starting material) is at the resonance area of 1.6 to 1.52 ppm.
Consider relative intensity, according to below equation (IX) by polymer-bonded the carbonic ester (" line in reactant mixture
Property carbonic ester " LC) it is scaled mol%
Weight content (weight according to the polymer-bonded carbonic ester (LC') in public formula (X) calculating reactant mixture
Amount %):
(X)
Wherein according to the value of formula (XI) calculating N (" denominator " N):
(XI)
Coefficient 102 is by CO2Molal weight (molal weight 44 g/mol) and the molal weight (molal weight of expoxy propane
58 g/mol) summation produce, coefficient 58 by expoxy propane molal weight produce, coefficient 146 is by the starting material 1,8-used
The molal weight of ethohexadiol produces.
Weight content (weight %) according to the cyclic carbonate (CC') in formula (XII) calculating reactant mixture:
(XII)
The value of N is wherein calculated according to formula (XI).
In order to be calculated based on polymers compositions (by without CO by the value that forms of reactant mixture2Under the conditions of the work that carries out
The polyether polyol synthesized by starting material and expoxy propane during changing step, and at CO2In the presence of during the activation step that carries out
Form with the polyether carbonate polyol synthesized by starting material, expoxy propane and carbon dioxide during copolymerization) form, by meter
Calculate non-polymeric ingredients (the most ring-type propylene carbonate and the unreacted epoxy third that may be present rejecting reactant mixture
Alkane).By means of coefficient F=44/ (44+58), by the weight content conversion of carbonate repetitive unit in polyether carbonate polyol
Weight content for carbon dioxide.CO in polyether carbonate polyol2The indicating value (" CO of introducing of content2”;See following reality
Execute example and table 1) it is standardized as at CO2In the presence of copolymerization and optional activation step in formed polyether carbonate polyol molecule
Ratio (i.e. do not consider at this to come from starting material (1,8-ethohexadiol) and starting material with without CO2Under the conditions of add epoxidation
The ratio of the polyether carbonate polyol molecule of the reaction of thing).
The H-functional initiator compound used:
1,8-ethohexadiol Sigma Aldrich.
Embodiment 1 to 7: catalyst preparation is as follows:
Embodiment 1 (contrast): prepare dmc catalyst under without NaOH
Use and prepare catalyst according to the device of Fig. 4 of WO-A 01/39883.
Loop at the injection disperser comprising the Fig. 2 according to WO-A 01/39883 with boring (diameter 0.7 mm)
In reactor, at 50 DEG C, circulate the zinc chloride of the 258 g solution in the distilled water of 937 g and the tert-butyl alcohol of 135 g.Xiang Qi
The Cobalt Potassium Cyanide (0.078 mol) of 26 g solution in the distilled water of 332 g is added in middle metering.Pressure in injection disperser
Power loss is 2.5 bar.Then under the pressure loss in the injection disperser of 50 DEG C and 2.5 bar, the dispersion of formation is followed
Ring 60 minutes.Thereafter, the tert-butyl alcohol of 5.7 g, the distilled water of 159 g and the mixing of the polypropylene glycol 1000 of 27.6 g are added in metering
Thing, then circulates dispersion 80 minutes at 50 DEG C under the pressure loss in the injection disperser of 50 DEG C and 2.5 bar.
There are 20 cm3Filter area nutsch filter in filter the dispersions obtained of 230 g, then with 82 g's
The tert-butyl alcohol, the mixture washing of the distilled water of 42.3 g and the polypropylene glycol 1000 of 1.7 g.Mechanical presses between two filter paper
The filter cake of washing, and be finally dried 2 hours at 60 DEG C under the fine vacuum of about 0.05 bar (definitely).
Embodiment 2 (contrast): with every mol Cobalt Potassium Cyanide, 0.25 mol alkali equivalent prepares dmc catalyst
Use and prepare catalyst according to the device of Fig. 4 of WO-A 01/39883.
Loop at the injection disperser comprising the Fig. 2 according to WO-A 01/39883 with boring (diameter 0.7 mm)
In reactor, at 50 DEG C, circulate the zinc chloride distilled water at 937 g of 258 g, the tert-butyl alcohol of 135 g and the 10% of 7.8 g
Solution in NaOH aqueous solution (0.0195 mol alkali equivalent).The Cobalt Potassium Cyanide (0.078 of 26 g is added in metering wherein
Mol) solution in the distilled water of 332 g.The pressure loss in injection disperser is 2.5 bar.Then at 50 DEG C and 2.5
Under the pressure loss in the injection disperser of bar, the dispersion formed is circulated 60 minutes.Thereafter, the uncle of 5.7 g is added in metering
Butanol, the distilled water of 159 g and the mixture of the polypropylene glycol 1000 of 27.6 g, then the injection at 50 DEG C and 2.5 bar divides
Dissipate and under the pressure loss in device, dispersion is circulated 80 minutes.
There are 20 cm3Filter area nutsch filter in filter the dispersions obtained of 230 g, then with 82 g's
The tert-butyl alcohol, the mixture washing of the distilled water of 42.3 g and the polypropylene glycol 1000 of 1.7 g.Mechanical presses between two filter paper
The filter cake of washing, and be finally dried 2 hours at 60 DEG C under the fine vacuum of about 0.05 bar (definitely).
Embodiment 3: with every mol Cobalt Potassium Cyanide, 0.55 mol alkali equivalent prepares dmc catalyst
By the Cobalt Potassium Cyanide of 7.4 g (0.022 mol), the solution of the tert-butyl alcohol of 39 g and the distilled water of 302 g is in advance
Put into 1-to rise in round-bottomed flask, and by means of laboratory stirrer (1000 turns every point), accompanied by intense is heated with stirring to 30 DEG C.
During 3 minutes, drip in agitating solution 152 g 50% solder(ing)acid (alkaline 0.64 weight % ZnO, quite
In 0.012 mol alkali equivalent).Then in 30 DEG C of further stirrings 30 minutes (1000 turns every point).Shape is filtered by means of nutsch filter
The suspension become.Then in the mixture of the tert-butyl alcohol of 110 g and the distilled water of 60 g accompanied by intense stirring (1000 turns every
Point) disperse the wet cake of 8.0 g.When all solids is dispersed in wash solution, stirring 30 minutes further.Again borrow
Help nutsch filter and filter suspension, in the tert-butyl alcohol of 144 g, the most again disperse wet cake.After filtering dispersion, very
In the air (300 mbar), by filtration cakes torrefaction one night at 45 DEG C.
Embodiment 4: prepare dmc catalyst with every mol Cobalt Potassium Cyanide 0.372 mol alkali equivalent
Use and prepare catalyst according to the device of Fig. 4 of WO-A 01/39883.
Loop at the injection disperser comprising the Fig. 2 according to WO-A 01/39883 with boring (diameter 0.7 mm)
In reactor, at 50 DEG C, circulate the zinc chloride distilled water at 937 g of 258 g, the tert-butyl alcohol of 135 g and the 10% of 15.3 g
Solution in aqueous sodium carbonate (0.0145 mol).The Cobalt Potassium Cyanide (0.078 mol) of metering interpolation 26 g exists wherein
Solution in the distilled water of 332 g.The pressure loss in injection disperser is 2.5 bar.Then 50 DEG C and the spray of 2.5 bar
Penetrate and under the pressure loss in disperser, the dispersion formed is circulated 60 minutes.Thereafter, the tert-butyl alcohol of metering interpolation 5.7 g, 159
The distilled water of g and the mixture of the polypropylene glycol 1000 of 27.6 g, the then pressure in the injection disperser of 50 DEG C and 2.5 bar
At 50 DEG C, dispersion is circulated 80 minutes under power loss.There are 20 cm3Filter area nutsch filter in filter 230 g
Dispersions obtained, then with the tert-butyl alcohol of 82 g, the mixture of the distilled water of 42.3 g and the polypropylene glycol 1000 of 1.7 g is washed
Wash.The filter cake of mechanical presses washing between two filter paper, and final at 60 DEG C under the fine vacuum of about 0.05 bar (definitely)
It is dried 2 hours.
Embodiment 5 (contrast): prepare dmc catalyst with every mol Cobalt Potassium Cyanide 0.20 mol alkali equivalent
Use and prepare catalyst according to the device of Fig. 4 of WO-A 01/39883.
Loop at the injection disperser comprising the Fig. 2 according to WO-A 01/39883 with boring (diameter 0.7 mm)
In reactor, at 50 DEG C, circulate the zinc chloride distilled water at 937 g of 258 g, the tert-butyl alcohol of 135 g and the 10% of 15.3 g
Solution in carbonic acid mono-methyl sodium water solution (0.0156 mol).The Cobalt Potassium Cyanide (0.078 of 26 g is added in metering wherein
Mol) solution in the distilled water of 332 g.The pressure loss in injection disperser is 2.5 bar.Then at 50 DEG C and 2.5
Under the pressure loss in the injection disperser of bar, the dispersion formed is circulated 60 minutes.Thereafter, the uncle of 5.7 g is added in metering
Butanol, the distilled water of 159 g and the mixture of the polypropylene glycol 1000 of 27.6 g, then the injection at 50 DEG C and 2.5 bar divides
Dissipate and under the pressure loss in device, dispersion is circulated 80 minutes.
There are 20 cm3Filter area nutsch filter in filter the dispersions obtained of 230 g, then with 82 g's
The tert-butyl alcohol, the mixture washing of the distilled water of 42.3 g and the polypropylene glycol 1000 of 1.7 g.Mechanical presses between two filter paper
The filter cake of washing, and be finally dried 2 hours at 60 DEG C under the fine vacuum of about 0.05 bar (definitely).
Embodiment 6: prepare dmc catalyst with every mol Cobalt Potassium Cyanide 1.25 mol alkali equivalent
Use and prepare catalyst according to the device of Fig. 4 of WO-A 01/39883.
Loop at the injection disperser comprising the Fig. 2 according to WO-A 01/39883 with boring (diameter 0.7 mm)
In reactor, at 50 DEG C, circulate the zinc bromide distilled water at 937 g of 427 g, the tert-butyl alcohol of 135 g and the 10% of 39.0 g
Solution in NaOH aqueous solution (0.0975 mol).Metering adds the Cobalt Potassium Cyanide (0.078 mol) of 26 g 332 wherein
Solution in the distilled water of g.The pressure loss in injection disperser is 2.5 bar.Then the injection at 50 DEG C and 2.5 bar divides
Dissipate and under the pressure loss in device, the dispersion formed is circulated 60 minutes.Thereafter, the tert-butyl alcohol of 5.7 g is added in metering, 159 g's
The mixture of the polypropylene glycol 1000 of distilled water and 27.6 g, the then pressure in the injection disperser of 50 DEG C and 2.5 bar
Under loss, dispersion is circulated 80 minutes.
There are 20 cm3Filter area nutsch filter in filter the dispersions obtained of 230 g, then with 82 g's
The tert-butyl alcohol, the mixture washing of the distilled water of 42.3 g and the polypropylene glycol 1000 of 1.7 g.Mechanical presses between two filter paper
The filter cake of washing, and be finally dried 2 hours at 60 DEG C under the fine vacuum of about 0.05 bar (definitely).
Embodiment 7 (contrast): prepare dmc catalyst with every mol Cobalt Potassium Cyanide 2.0 mol alkali equivalent
Use and prepare catalyst according to the device of Fig. 4 of WO-A 01/39883.
Loop at the injection disperser comprising the Fig. 2 according to WO-A 01/39883 with boring (diameter 0.7 mm)
In reactor, at 50 DEG C, circulate the zinc bromide distilled water at 937 g of 427 g, the tert-butyl alcohol of 135 g and the 10% of 62.4 g
Solution in NaOH aqueous solution (0.156 mol).Metering adds the Cobalt Potassium Cyanide (0.078 mol) of 26 g 332 wherein
Solution in the distilled water of g.The pressure loss in injection disperser is 2.5 bar.Then the injection at 50 DEG C and 2.5 bar divides
Dissipate and under the pressure loss in device, the dispersion formed is circulated 60 minutes.Thereafter, the tert-butyl alcohol of 5.7 g is added in metering, 159 g's
The mixture of the polypropylene glycol 1000 of distilled water and 27.6 g, the then pressure in the injection disperser of 50 DEG C and 2.5 bar
Under loss, dispersion is circulated 80 minutes.
There are 20 cm3Filter area nutsch filter in filter the dispersions obtained of 230 g, then with 82 g's
The tert-butyl alcohol, the mixture washing of the distilled water of 42.3 g and the polypropylene glycol 1000 of 1.7 g.Mechanical presses between two filter paper
The filter cake of washing, and be finally dried 2 hours at 60 DEG C under the fine vacuum of about 0.05 bar (definitely).
Embodiment 8 to 14: test catalyst as follows in prepared by polyether carbonate polyol:
By the dry dmc catalyst (seeing table 1 below) according to one of embodiment 1 to 7 of 141 mg and being dried of 51 g
1,8-ethohexadiol (starting material) is placed in advance in having the 1-of gas-measuring equipment and rises in pressurized reactor.Reactor is heated to
130 DEG C, by being repeatedly inflated to about 5 bar with nitrogen and being decompressed to about 1 bar subsequently and carry out deactivation.This process carries out 3 times.?
130 DEG C and there is no CO2In the presence of, by the expoxy propane (PO) of 25 g rapidly metering addition reactor.Temperature peak (" heat
Point ") and pressure drop to initial pressure (about 1 bar) indicate activation of catalyst.After first time pressure drop, quick metering adds 20 g
PO, and the PO of then 19 g, in every case, there is temperature peak and pressure drop again in result.It has been filled with 50 at reactor
The CO of bar2Afterwards, quick metering adds the PO of 50 g, temperature peak occurs after the waiting time [time 1].Meanwhile, dioxy
Change carbon CO2Pressure begins to decline.So regulate pressure so that add new CO when pressure drops under rated value2.Until that
Time, with about 1.8 g/min, remaining expoxy propane (435 g) is continuously pumped in reactor, and after 10 minutes, by temperature with
Within every five minutes, the step of 5 DEG C drops to 105 DEG C.After terminating metering interpolation PO, at 105 DEG C, continuation stirring under above-mentioned pressure (1,
500 turns every point), until not observing further CO2Consume.
Table 1: prepare polyether carbonate polyol
Embodiment | Use the catalyst of embodiment from below | Alkalescence [every mol K3[Co(CN)6], mol alkali equivalent] | Time 1 [min] | The CO introduced2[weight %] | Selectivity is ring-type/linear | Hydroxyl value [mg/g] | Polydispersity |
8 (contrasts) | 1 (contrast) | -- | 30 | 21.0 | 0.20 | 65.5 | 1.70 |
9 (contrasts) | 2 (contrasts) | 0.25 | 38 | 21.0 | 0.21 | 64.6 | 1.52 |
10 | 3 | 0.55 | 74 | 19.3 | 0.16 | 66.6 | 1.68 |
11 | 4 | 0.372 | 58 | 18.7 | 0.17 | 65.3 | 1.52 |
12 (contrasts) | 5 (contrasts) | 0.20 | 114 | 22.4 | 0.22 | 75.2 | 1.91 |
13 | 6 | 1.25 | 50 | 18.8 | 0.14 | 48.7 * | 1.44 |
14 (contrasts) | 7 (contrasts) | 2.0 | 188 | 18.5 | 0.14 | 57.3 * | 1.59 |
Contrast=comparative example
*) hydroxyl value of reactant mixture, the propylene carbonate of formation separates the most in advance.
From the result of table 1 it is clear that relative to there is no the dmc catalyst of alkali that adds, it is achieved selectivity improves to be needed
Want the alkali of minimum flow.Such as, in prepared by dmc catalyst, the K of every mol3[Co(CN)6] add 0.2 (embodiment 12 (contrast)
Or the alkali equivalent of 0.25 (embodiment 9 (contrast)) does not improve the selectivity without alkali (embodiment 8 (contrast)).The most every
The K of mol3[Co(CN)6], more than 0.25 alkali equivalent, such as according to the K of the every mol of embodiment 113[Co(CN)6], 0.37 alkali equivalent
Alkalescence, selectivity improves to being conducive to required linear polyether carbonate polyol direction.On the other hand, too high every mol's
K3[Co(CN)6] the economy of alkali injury equivalency method;The K of even every mol3[Co(CN)6], 2.0 mol alkali equivalents have made
Time 1 extends more than 120 minutes (embodiment 14 (contrast)).
Claims (11)
1. in the presence of at least one DMC catalysts by one or more H-functional starter substances, one or more
Alkylene oxide and carbon dioxide prepare the method for polyether carbonate polyol, are wherein used for preparing described DMC catalysts
Cyanide-free slaine, six cyanogen cobalts (III) acid potassium or above-mentioned both salt comprise the alkali equivalent of 0.3 to 1.8 mol, based on 1
Mol by synthesize this catalyst six cyanogen cobalts (III) acid potassium based on alkalescence metal hydroxides, metal carbonate and/or
Metal-oxide, it is characterised in that by, in the presence of one or more organic complex parts, making cyanide-free slaine
The reactant aqueous solution of aqueous solution and six cyanogen cobalts (III) acid potassium prepares dmc catalyst, the metallic hydrogen of one or more of which alkalescence
Oxide, metal carbonate and/or metal-oxide are present in the aqueous solution of described cyanide-free slaine, described six cyanogen cobalts
(III) in the acid aqueous solution of potassium or both aqueous solutions, and wherein use the metal hydroxides of alkalescence, metal carbonate
And/or the alkali equivalent that the summation of metal-oxide is 0.3 to 1.8 mol, six cyanogen for synthesizing this catalyst based on 1 mol
Cobalt (III) acid potassium meter.
Method the most according to claim 1, wherein dmc catalyst is prepared by the following manner:
I () in the first step, in the presence of one or more organic complex parts, makes the aqueous solution of cyanide-free slaine
With the reactant aqueous solution of six cyanogen cobalt (III) acid potassium, the metal hydroxides of one or more of which alkalescence and/or metal carbonate
And/or metal-oxide is present in the aqueous solution of described cyanide-free slaine, the aqueous solution of described six cyanogen cobalt (III) acid potassium
In or both aqueous solutions in, and the metal hydroxides of the alkalescence wherein used and/or metal carbonate and/or burning
The summation of thing is 0.3 to 1.8 mol alkali equivalent, based on 1 mol based on the metal cyanide salt synthesizing this catalyst,
(ii) wherein in second step, from the suspension obtained by (i), solid is separated,
(iii) the most in the third step, the solid separated with the solution washing of organic complex part,
(iv) the most then gained solid is dried,
Add one or more organic complex parts the most in the first step, or in second step, precipitate double metal cyanide
One or more organic complex parts are added at once after compound.
3. according to the method for claim 1 or 2, wherein for prepare DMC catalysts cyanide-free slaine,
Six cyanogen cobalt (III) acid potassium or above-mentioned both salt comprise metal hydroxides, metal carbonate and/or the metal-oxide of alkalescence
0.6 to 1.6 mol alkali equivalent of form, based on 1 mol based on six cyanogen cobalt (III) the acid potassium synthesizing this catalyst.
4. according to the method for claim 1 or 2, metal hydroxides, metal carbonate and/or the metal of the alkalescence wherein used
At least one among the oxide of metal, carbonate or the hydroxide of 1a and the 2a race of the periodic table of elements of oxide.
Method the most according to claim 4, metal hydroxides, metal-oxide and/or the metal carbon of the alkalescence wherein used
Hydrochlorate is among sodium carbonate, sodium hydroxide, potassium hydroxide, potassium carbonate, calcium oxide, calcium hydroxide, barium hydroxide and Barium monoxide
At least one.
6., according to the method for claim 1 or 2, the cyanide-free slaine being wherein used for being formed DMC compound is selected from zinc chloride,
Zinc bromide, zinc iodide, zinc acetate, acetopyruvic acid zinc, Zinc dibenzoate., zinc nitrate, iron sulfate (II), ferric bromide (II), chlorination
At least one among ferrum (II), cobaltous chloride (II), Cobaltous rhodanide (II), Nickel dichloride. (II) and nickel nitrate (II).
7. according to the method for claim 1 or 2, it is characterised in that
(α) by H-functional starter substance, or the mixture of at least two H-functional starter substance is placed in reaction vessel, and
Optionally through heating up and/or water and/or other effumability compound are removed in decompression, the most before the drying or afterwards, to H-
Functional starter substance, or the mixture of at least two H-functional starter substance are added described dmc catalyst,
(β) in order to activate
(β 1), in first activation step, adds the first of one or more alkylene oxides in the mixture coming from step (α)
Partial amount, total amount meter based on the alkylene oxide amount used in activation and copolymerization, and the most then observe one period of waiting time, until
Due to follow-up heat-producing chemical reaction, temperature peak occurs, and/or reactor occurs pressure drop,
(β 2) in second activation step, after activation step previously reaches temperature peak, to coming from previous activation
The mixture of step adds the Part II amount of one or more alkylene oxides, based on the alkylene oxide amount used in activation and copolymerization
Total amount, and the most then observing one period of waiting time, until temperature peak occurs due to follow-up heat-producing chemical reaction,
And/or reactor occurs pressure drop,
(γ) one or more alkylene oxides and carbon dioxide are added in the mixture coming from step (β).
Method the most according to claim 7, it is characterised in that alkylene oxide and carbon dioxide are in the pressure copolymerization of 1 to 200 bar.
Method the most according to claim 7, it is characterised in that alkylene oxide and carbon dioxide are common the temperature range of 60 to 150 DEG C
Poly-.
Method the most according to claim 7, it is carried out in tubular reactor, stirred tank or loop reactor.
11. methods according to claim 7, it is carried out in stirred tank, it is characterised in that in step (γ), during reaction
One or more H-functional initiator compounds are continuously metered in described stirred tank.
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